Naphthalene isoxazoline compounds for controlling invertebrate pests

ABSTRACT

Disclosed are compounds of Formula 1, 
                         
wherein
 
     J is 
                         
and R 1a , R 1b , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 14 , R 15 , R 16 , Q and X are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or a composition of the invention.

FIELD OF THE INVENTION

This invention relates to certain isoxazoline compounds and compositionssuitable for agronomic and nonagronomic uses, and methods of their usefor controlling invertebrate pests such as arthropods in both agronomicand nonagronomic environments.

BACKGROUND OF THE INVENTION

The control of invertebrate pests is extremely important in achievinghigh crop efficiency. Damage by invertebrate pests to growing and storedagronomic crops can cause significant reduction in productivity andthereby result in increased costs to the consumer. The control ofinvertebrate pests in forestry, greenhouse crops, ornamentals, nurserycrops, stored food and fiber products, household, turf, wood products,and public health is also important. Many products are commerciallyavailable for these purposes, but the need continues for new compoundsthat are more effective, less costly, less toxic, environmentally saferor have different sites of action.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula 1, compositionscontaining them, and their use for controlling invertebrate pests:

wherein

-   -   J is C₂-C₄ alkyl substituted with one cyano; —CH₂(cyclopropyl)        substituted with one cyano; or cyclopropyl, unsubstituted or        substituted with one cyano or one C(O)NHR¹⁷; or    -   J is

-   -   R^(1a) is Cl or CF₃;    -   R^(1b) is H or Cl;    -   R² is C₁-C₄ alkyl, unsubstituted or substituted with        substituents independently selected from cyano, nitro, OR⁹,        S(O)_(n)R¹⁰, CO₂R¹¹ and C(O)NR¹²R¹³;    -   R³ is H; or C₁-C₄ alkyl, unsubstituted or substituted with        substituents independently selected from cyano, nitro, OR⁹,        S(O)_(n)R¹⁰, CO₂R¹¹ and C(O)NR¹²R¹³;    -   R⁴ is H, C₁-C₄ alkyl or C₁-C₄ haloalkyl;    -   R⁵ is H or C₁-C₄ alkyl;    -   R⁶ is H or C₁-C₄ alkyl;    -   R⁷ is H, C₁-C₄ alkyl or C₁-C₄ haloalkyl;    -   X is —O— or —C(O)—;    -   R⁸ is H, C₁-C₄ alkyl, C₁-C₄ haloalkyl or C₃-C₆ cycloalkyl;    -   each R⁹, R¹⁰, R¹¹, R¹² and R¹³ is independently H or C₁-C₄        alkyl;    -   R¹⁴ is H; or C₁-C₄ alkyl, unsubstituted or substituted with        substituents independently selected from cyano, nitro, OR⁹,        S(O)_(n)R¹⁰, CO₂R¹¹ and C(O)NR¹²R¹³;    -   R¹⁵ is H, C₁-C₄ alkyl or C₁-C₄ haloalkyl;    -   R¹⁶ is fluoro, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₆ alkoxy, C₁-C₆        haloalkoxy, amino or C₁-C₆ alkylamino;    -   R¹⁷ is H, C₁-C₄ alkyl, C₁-C₄ haloalkyl or C₃-C₆ cycloalkyl;    -   Q is pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl,        1,2,4-triazinyl, 1,3,5-triazinyl, furanyl, thienyl, pyrrolyl,        pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl,        tetrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl,        1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl,        1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl or 1,3,4-thiadiazolyl,        each unsubstituted or substituted with substituents        independently selected from cyano, nitro, halogen, C₁-C₄ alkyl,        C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄        alkylthio, C₁-C₄ haloalkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄        haloalkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylsulfonyl,        C₂—O₅ alkoxycarbonyl, C₂—O₅ alkylaminocarbonyl and C₃—O₅        dialkylaminocarbonyl; and    -   each n is independently 0, 1 or 2.

This invention also provides a composition comprising a compound ofFormula 1 and at least one additional component selected from the groupconsisting of surfactants, solid diluents and liquid diluents. In oneembodiment, this invention also provides a composition for controllingan invertebrate pest comprising a compound of Formula 1 and at least oneadditional component selected from the group consisting of surfactants,solid diluents and liquid diluents, said composition optionally furthercomprising at least one additional biologically active compound oragent.

This invention provides a method for controlling an invertebrate pestcomprising contacting the invertebrate pest or its environment with abiologically effective amount of a compound of Formula 1 (e.g., as acomposition described herein). This invention also relates to suchmethod wherein the invertebrate pest or its environment is contactedwith a composition comprising a biologically effective amount of acompound of Formula 1, and at least one additional component selectedfrom the group consisting of surfactants, solid diluents and liquiddiluents, said composition optionally further comprising a biologicallyeffective amount of at least one additional biologically active compoundor agent.

This invention also provides a method for protecting a seed from aninvertebrate pest comprising contacting the seed with a biologicallyeffective amount of a compound of Formula 1 (e.g., as a compositiondescribed herein). This invention also relates to the treated seed.

This invention also provides a method for increasing vigor of a cropplant comprising contacting the crop plant, the seed from which the cropplant is grown or the locus (e.g., growth medium) of the crop plant witha biologically effective amount of a compound of Formula 1 (e.g., as acomposition described herein).

DETAILS OF THE INVENTION

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” “contains”, “containing,” “characterizedby” or any other variation thereof, are intended to cover anon-exclusive inclusion, subject to any limitation explicitly indicated.For example, a composition, mixture, process or method that comprises alist of elements is not necessarily limited to only those elements butmay include other elements not expressly listed or inherent to suchcomposition, mixture, process or method.

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim, such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistingof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition or method that includes materials, steps, features,components, or elements, in addition to those literally disclosed,provided that these additional materials, steps, features, components,or elements do not materially affect the basic and novelcharacteristic(s) of the claimed invention. The term “consistingessentially of” occupies a middle ground between “comprising” and“consisting of”.

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso describe such an invention using the terms “consisting essentiallyof” or “consisting of.”

Further, unless expressly stated to the contrary, “or” refers to aninclusive or and not to an exclusive or. For example, a condition A or Bis satisfied by any one of the following: A is true (or present) and Bis false (or not present), A is false (or not present) and B is true (orpresent), and both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element orcomponent of the invention are intended to be nonrestrictive regardingthe number of instances (i.e. occurrences) of the element or component.Therefore “a” or “an” should be read to include one or at least one, andthe singular word form of the element or component also includes theplural unless the number is obviously meant to be singular.

As referred to in this disclosure, the term “invertebrate pest” includesarthropods, gastropods, nematodes and helminths of economic importanceas pests. The term “arthropod” includes insects, mites, spiders,scorpions, centipedes, millipedes, pill bugs and symphylans. The term“gastropod” includes snails, slugs and other Stylommatophora. The term“nematode” includes members of the phylum Nematoda.

In the context of this disclosure “invertebrate pest control” meansinhibition of invertebrate pest development (including mortality,feeding reduction, and/or mating disruption), and related expressionsare defined analogously.

The term “agronomic” refers to the production of field crops such as forfood and fiber and includes the growth of maize or corn, soybeans andother legumes, rice, cereal (e.g., wheat, oats, barley, rye and rice),leafy vegetables (e.g., lettuce, cabbage, and other cole crops),fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers andcucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g.,pome, stone and citrus), small fruit (e.g., berries and cherries) andother specialty crops (e.g., canola, sunflower and olives).

The term “nonagronomic” refers to other than field crops, such ashorticultural crops (e.g., greenhouse, nursery or ornamental plants notgrown in a field), residential, agricultural, commercial and industrialstructures, turf (e.g., sod farm, pasture, golf course, lawn, sportsfield, etc.), wood products, stored product, agro-forestry andvegetation management, and public health applications.

The term “crop vigor” refers to rate of growth or biomass accumulationof a crop plant. An “increase in vigor” refers to an increase in growthor biomass accumulation in a crop plant relative to an untreated controlcrop plant. The term “crop yield” refers to the return on crop material,in terms of both quantity and quality, obtained after harvesting a cropplant. An “increase in crop yield” refers to an increase in crop yieldrelative to an untreated control crop plant.

The term “biologically effective amount” refers to the amount of abiologically active compound (e.g., a compound of Formula 1) sufficientto produce the desired biological effect when applied to (i.e. contactedwith) an invertebrate pest to be controlled or its environment, or to aplant, the seed from which the plant is grown, or the locus of the plant(e.g., growth medium) to protect the plant from injury by theinvertebrate pest or for other desired effect (e.g., increasing plantvigor).

In the above recitations, the term “alkyl”, used either alone or incompound words such as “alkylthio” or “haloalkyl” includesstraight-chain or branched alkyl, such as, methyl, ethyl, n-propyl,i-propyl, or the different butyl, pentyl or hexyl isomers.

“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy,isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.“Alkylthio” includes branched or straight-chain alkylthio moieties suchas methylthio, ethylthio, and the different propylthio, butylthio,pentylthio and hexylthio isomers.

The term “halogen”, either alone or in compound words such as“haloalkyl”, or when used in descriptions such as “alkyl substitutedwith halogen” includes fluorine, chlorine, bromine or iodine. Further,when used in compound words such as “haloalkyl”, or when used indescriptions such as “alkyl substituted with halogen” said alkyl may bepartially or fully substituted with halogen atoms which may be the sameor different. Examples of “haloalkyl” or “alkyl substituted withhalogen” include F₃C—, ClCH₂—, CF₃CH₂— and CF₃CCl₂—.

The chemical abbreviations S(O) and S(═O) as used herein represent asulfinyl moiety. The chemical abbreviations SO₂, S(O)₂ and S(═O)₂ asused herein represent a sulfonyl moiety. The chemical abbreviations C(O)and C(═O) as used herein represent a carbonyl moiety. The chemicalabbreviations CO₂, C(O)O and C(═O)O as used herein represent anoxycarbonyl moiety.

A dashed line in a structure fragment denotes the attachment point ofthe fragment to the remainder of the molecule. For example, when thevariable J in Formula 1 is defined as J-1, the dashed line in thestructure of J-1 means that J-1 is attached to the remainder of thestructure of Formula 1 at that position, as shown below.

The variable X in J-4 is defined as —O— or —C(O)—, and this means thatJ-4 is as shown below.

When the variable J is defined as —CH₂(cyclopropyl) substituted with onecyano, this means that J is as shown below (i.e. the cyano group can beattached to either the methylene group or to any carbon atom of thecyclopropyl ring).

The total number of carbon atoms in a substituent group is indicated bythe “C_(i)-C_(j)” prefix. For example, C₁-C₄ alkyl designates methyl,ethyl, and the various propyl and butyl isomers.

When a compound is substituted with a substituent bearing a subscriptthat indicates the number of said substituents can exceed 1, saidsubstituents (when they exceed 1) are independently selected from thegroup of defined substituents. Further, when the subscript indicates arange, e.g. (R)_(i-j), then the number of substituents may be selectedfrom the integers between i and j inclusive. When a group contains asubstituent which can be hydrogen, then when this substituent is takenas hydrogen, it is recognized that this is equivalent to said groupbeing unsubstituted. When one or more positions on a group are said tobe “not substituted” or “unsubstituted”, then hydrogen atoms areattached to take up any free valency.

When a substituent is a 5- or 6-membered nitrogen-containingheterocyclic ring, it may be attached to the remainder of Formula 1though any available carbon or nitrogen ring atom, unless otherwisedescribed.

A wide variety of synthetic methods are known in the art to enablepreparation of aromatic and nonaromatic heterocyclic rings and ringsystems; for extensive reviews see the eight volume set of ComprehensiveHeterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief,Pergamon Press, Oxford, 1984 and the twelve volume set of ComprehensiveHeterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V.Scriven editors-in-chief, Pergamon Press, Oxford, 1996.

Compounds of this invention can exist as one or more stereoisomers.Stereoisomers are isomers of identical constitution but differing in thearrangement of their atoms in space and include enantiomers,diastereomers, cis-trans isomers (also known as geometric isomers) andatropisomers. Atropisomers result from restricted rotation about singlebonds where the rotational barrier is high enough to permit isolation ofthe isomeric species. One skilled in the art will appreciate that onestereoisomer may be more active and/or may exhibit beneficial effectswhen enriched relative to the other stereoisomer(s) or when separatedfrom the other stereoisomer(s). Additionally, the skilled artisan knowshow to separate, enrich, and/or to selectively prepare saidstereoisomers. For a comprehensive discussion of all aspects ofstereoisomerism, see Ernest L. Eliel and Samuel H. Wilen,Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

Compounds selected from Formula 1 typically exist in more than one form,and Formula 1 thus includes all crystalline and non-crystalline forms ofthe compounds that Formula 1 represents. Non-crystalline forms includeembodiments which are solids such as waxes and gums as well asembodiments which are liquids such as solutions and melts. Crystallineforms include embodiments which represent essentially a single crystaltype and embodiments which represent a mixture of polymorphs (i.e.different crystalline types). The term “polymorph” refers to aparticular crystalline form of a chemical compound that can crystallizein different crystalline forms, these forms having differentarrangements and/or conformations of the molecules in the crystallattice. Although polymorphs can have the same chemical composition,they can also differ in composition due to the presence or absence ofco-crystallized water or other molecules, which can be weakly orstrongly bound in the lattice. Polymorphs can differ in such chemical,physical and biological properties as crystal shape, density, hardness,color, chemical stability, melting point, hygroscopicity,suspensibility, dissolution rate and biological availability. Oneskilled in the art will appreciate that a polymorph of a compoundrepresented by Formula 1 can exhibit beneficial effects (e.g.,suitability for preparation of useful formulations, improved biologicalperformance) relative to another polymorph or a mixture of polymorphs ofthe same compound represented by Formula 1. Preparation and isolation ofa particular polymorph of a compound represented by Formula 1 can beachieved by methods known to those skilled in the art including, forexample, crystallization using selected solvents and temperatures.Compounds of this invention may exist as one or more crystallinepolymorphs. This invention comprises both individual polymorphs andmixtures of polymorphs, including mixtures enriched in one polymorphrelative to others. For a comprehensive discussion of polymorphism seeR. Hilfiker, Ed., Polymorphism In the Pharmaceutical Industry,Wiley-VCH, Weinheim, 2006.

Embodiments of the present invention as described in the Summary of theInvention include those described below. In the following Embodiments,reference to “a compound of Formula 1” includes the definitions ofsubstituents specified in the Summary of the Invention unless furtherdefined in the Embodiments.

-   -   Embodiment 1. A compound of Formula 1 wherein J is J-1.    -   Embodiment 1a. A compound of Embodiment 1 wherein R² is C₁-C₄        alkyl, unsubstituted or substituted with substituents        independently selected from OMe, SMe, S(O)Me and SO₂Me.    -   Embodiment 1b. A compound of Embodiment 1a wherein R² is C₁-C₄        alkyl substituted with OMe, SMe, S(O)Me or SO₂Me.    -   Embodiment 1c. A compound of Embodiment 1a wherein R² is C₁-C₄        alkyl.    -   Embodiment 1d. A compound of Embodiment 1c wherein R² is methyl.    -   Embodiment 1e. A compound of any of Embodiments 1-1d wherein R³        is H or methyl.    -   Embodiment 1f. A compound of any of Embodiments 1-1d wherein R⁴        is H, C₁-C₂ alkyl or C₁-C₂ haloalkyl.    -   Embodiment 2. A compound of Formula 1 wherein J is J-2.    -   Embodiment 2a. A compound of Embodiment 2 or 2a wherein R⁵ is H        or methyl.    -   Embodiment 2b. A compound of Embodiment 2a wherein R⁵ is methyl.    -   Embodiment 2c. A compound of Embodiment 2a wherein R⁵ is H.    -   Embodiment 2d. A compound of any of Embodiments 2-2c wherein Q        is pyridinyl or pyrimidinyl.    -   Embodiment 2e. A compound of Embodiment 2d wherein Q is        pyridinyl.    -   Embodiment 2f. A compound of Embodiment 2d wherein Q is        pyrimidinyl.    -   Embodiment 2g. A compound of any of Embodiments 2-2f wherein J-2        is

-   -   Embodiment 3. A composition consisting of a compound of Formula        1 wherein J is J-2a and a compound of Formula 1 wherein J is        J-2b

-   -   -   wherein the ratio of the compound of Formula 1 wherein J is            J-2a to the compound of Formula 1 wherein J is J-2b is            greater than 60:40.

    -   Embodiment 3a. A composition of Embodiment 3 wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 80:20.

    -   Embodiment 3b. A composition of Embodiment 3 wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 90:10.

    -   Embodiment 3c. A composition of Embodiment 3 wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 95:5.

    -   Embodiment 3d. A composition of Embodiment 3 wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 99:1.

    -   Embodiment 3e. A composition consisting of a compound of Formula        1 wherein J is J-2a and a compound of Formula 1 wherein J is        J-2b

-   -   -   and        -   R⁵ is methyl;        -   wherein the ratio of the compound of Formula 1 wherein J is            J-2a to the compound of Formula 1 wherein J is J-2b is            greater than 60:40.

    -   Embodiment 3f. A composition of Embodiment 3e wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 80:20.

    -   Embodiment 3g. A composition of Embodiment 3e wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 90:10.

    -   Embodiment 3h. A composition of Embodiment 3e wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 95:5.

    -   Embodiment 3i. A composition of Embodiment 3e wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 99:1.

    -   Embodiment 3j. A composition consisting of a compound of Formula        1 wherein J is J-2a and a compound of Formula 1 wherein J is        J-2b

-   -   -   and        -   Q is pyridinyl;        -   wherein the ratio of the compound of Formula 1 wherein J is            J-2a to the compound of Formula 1 wherein J is J-2b is            greater than 60:40.

    -   Embodiment 3k. A composition of Embodiment 3j wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 80:20.

    -   Embodiment 3l. A composition of Embodiment 3j wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 90:10.

    -   Embodiment 3m. A composition of Embodiment 3j wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 95:5.

    -   Embodiment 3n. A composition of Embodiment 3j wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 99:1.

    -   Embodiment 3o. A composition consisting of a compound of Formula        1 wherein J is J-2a and a compound of Formula 1 wherein J is        J-2b

-   -   -   and        -   Q is pyrimidinyl;        -   wherein the ratio of the compound of Formula 1 wherein J is            J-2a to the compound of Formula 1 wherein J is J-2b is            greater than 60:40.

    -   Embodiment 3p. A composition of Embodiment 3o wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 80:20.

    -   Embodiment 3q. A composition of Embodiment 3o wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 90:10.

    -   Embodiment 3r. A composition of Embodiment 3o wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 95:5.

    -   Embodiment 3s. A composition of Embodiment 3o wherein the ratio        of the compound of Formula 1 wherein J is J-2a to the compound        of Formula 1 wherein J is J-2b is greater than 99:1.

    -   Embodiment 4. A compound of Formula 1 wherein J is J-3.

    -   Embodiment 4a. A compound of Embodiment 4 wherein R⁶ is H.

    -   Embodiment 4b. A compound of Embodiment 4 wherein R⁷ is C₁-C₄        alkyl.

    -   Embodiment 4c. A compound of Embodiment 4b wherein R⁷ is methyl        or ethyl.

    -   Embodiment 4d. A compound of Embodiment 4c wherein R⁷ is methyl.

    -   Embodiment 5. A compound of Formula 1 or Embodiment 1 wherein J        is J-4.

    -   Embodiment 5a. A compound of Embodiment 5 wherein X is —O—.

    -   Embodiment 5b. A compound of Embodiment 5 wherein X is —C(O)—.

    -   Embodiment 5c. A compound of Embodiment 5, 5a or 5b wherein R⁸        is C₁-C₂ alkyl or C₁-C₂ haloalkyl.

    -   Embodiment 5d. A compound of Embodiment 5c wherein R⁸ is methyl        or ethyl.

    -   Embodiment 5e. A compound of Embodiment 5d wherein R⁸ is methyl.

    -   Embodiment 6. A compound of Formula 1 wherein J is J-5.

    -   Embodiment 6a. A compound of Embodiment 6 wherein R¹⁴ is C₁-C₄        alkyl.

    -   Embodiment 6b. A compound of Embodiment 6a wherein R¹⁴ is methyl        or ethyl.

    -   Embodiment 6c. A compound of Embodiment 6b wherein R¹⁴ is        methyl.

    -   Embodiment 6d. A compound of any of Embodiments 6-6c wherein R¹⁵        is C₁-C₄ alkyl.

    -   Embodiment 6e. A compound of Embodiment 6d wherein R¹⁴ is methyl        or ethyl.

    -   Embodiment 6f. A compound of Embodiment 6e wherein R¹⁴ is        methyl.

    -   Embodiment 6g. A compound of any of Embodiments 6-6f wherein J-5        is

-   -   Embodiment 7. A composition consisting of a compound of Formula        1 wherein J is J-5a and a compound of Formula 1 wherein J is        J-5b

-   -   -   wherein the ratio of the compound of Formula 1 wherein J is            J-5a to the compound of Formula 1 wherein J is J-5b is            greater than 60:40.

    -   Embodiment 7a. A composition of Embodiment 7 wherein the ratio        of the compound of Formula 1 wherein J is J-5a to the compound        of Formula 1 wherein J is J-5b is greater than 80:20.

    -   Embodiment 7b. A composition of Embodiment 7 wherein the ratio        of the compound of Formula 1 wherein J is J-5a to the compound        of Formula 1 wherein J is J-5b is greater than 90:10.

    -   Embodiment 7c. A composition of Embodiment 7 wherein the ratio        of the compound of Formula 1 wherein J is J-5a to the compound        of Formula 1 wherein J is J-5b is greater than 95:5.

    -   Embodiment 7b. A composition of Embodiment 7 wherein the ratio        of the compound of Formula 1 wherein J is J-5a to the compound        of Formula 1 wherein J is J-5b is greater than 99:1.

    -   Embodiment 8. A compound of Formula 1 wherein J is J-6.

    -   Embodiment 8a. A compound of Embodiment 8 wherein R¹⁶ is F,        methyl or amino

    -   Embodiment 8b. A compound of Embodiment 8a wherein R¹⁶ is        methyl.

    -   Embodiment 9. A compound of Formula 1 wherein J is C₂-C₄ alkyl        substituted with one cyano.

    -   Embodiment 9a. A compound of Embodiment 9 wherein J is ethyl        substituted with one cyano.

    -   Embodiment 9b. A compound of Embodiment 9a wherein J is        —CH(CN)CH₃.

    -   Embodiment 10. A compound of Formula 1 wherein J is        —CH₂(cyclopropyl) substituted with one cyano.

    -   Embodiment 10a. A compound of Embodiment 10 wherein J is        —CH(CN)(cyclopropyl).

    -   Embodiment 11. A compound of Formula 1 wherein J is cyclopropyl,        unsubstituted or substituted with one cyano or one C(O)NHR¹⁷.

    -   Embodiment 11a. A compound of Embodiment 11 wherein J is        cyclopropyl.

    -   Embodiment 11b. A compound of Embodiment 11 wherein J is        1-(cyano)cyclopropyl.

    -   Embodiment 11c. A compound of Formula 1 wherein J is C₂-C₄ alkyl        substituted with one cyano; or cyclopropyl.

    -   Embodiment 12. A compound of Formula 1 or any of Embodiments        1-11c wherein R^(1a) is Cl.

    -   Embodiment 12a. A compound of Formula 1 or any of Embodiments        1-11c wherein R^(1a) is CF₃.

    -   Embodiment 13. A compound of Formula 1 or any of Embodiments        1-12a wherein R^(1b) is H.

    -   Embodiment 13a. A compound of Formula 1 or any of Embodiments        1-12a wherein R^(1b) is Cl.

    -   Embodiment 14. A compound of Formula 1 or any of Embodiments        1-11c wherein R^(1a) is H and R^(1b) is CF₃.

    -   Embodiment 15. A compound of Formula 1 or any of Embodiments        1-11c wherein R^(1a) is Cl and R^(1b) is Cl.

    -   Embodiment 16. A compound of Formula 1 or any of Embodiments        1-11c wherein R^(1a) is Cl and R^(1b) is CF₃.

    -   Embodiment 17. A compound of Formula 1 or any of Embodiments        1-11c wherein R^(1a) is H and R^(1b) is CF₃, or R^(1a) is Cl and        R^(1b) is Cl, or R^(1a) is Cl and R^(1b) is CF₃.

    -   Embodiment 17a. A compound of Formula 1 or any of Embodiments        1-11c wherein R^(1a) is H and R^(1b) is CF₃, or R^(1a) is Cl and        R^(1b) is Cl.

    -   Embodiment 18. A composition consisting of a compound of Formula        1-1S and Formula 1-1R

-   -   -   wherein the ratio of the compound of Formula 1-1S to the            compound of Formula 1-1R is greater than 60:40.

    -   Embodiment 18a. A composition of Embodiment 18 wherein the ratio        of the compound of Formula 1-1S to the compound of Formula 1-1R        is greater than 80:20.

    -   Embodiment 18b. A composition of Embodiment 18 wherein the ratio        of the compound of Formula 1-1S to the compound of Formula 1-1R        is greater than 90:10.

    -   Embodiment 18c. A composition of Embodiment 18 wherein the ratio        of the compound of Formula 1-1S to the compound of Formula 1-1R        is greater than 95:5.

    -   Embodiment 18d. A composition of Embodiment 18 wherein the ratio        of the compound of Formula 1-1S to the compound of Formula 1-1R        is greater than 99:1.

    -   Embodiment 19. A composition consisting of a compound of Formula        1-1S and Formula 1-1R

-   -   -   wherein the ratio of the compound of Formula 1-1S to the            compound of Formula 1-1R is greater than 60:40.

    -   Embodiment 19a. A composition of Embodiment 19 wherein J is J-1.

    -   Embodiment 19b. A composition of Embodiment 19 wherein J is J-2.

    -   Embodiment 19c. A composition of Embodiment 19b wherein J is        J-2a

-   -   Embodiment 19d. A composition of Embodiment 19 wherein J is J-3.    -   Embodiment 19e. A composition of Embodiment 19 wherein J is J-4.    -   Embodiment 19f. A composition of Embodiment 19 wherein J is J-5.    -   Embodiment 19g. A composition of Embodiment 19f wherein J is        J-5a

-   -   Embodiment 19h. A composition of Embodiment 19 wherein J is J-6.    -   Embodiment 19i. A composition of Embodiment 19 wherein J is        C₂-C₄ alkyl substituted with one cyano.    -   Embodiment 19j. A composition of Embodiment 19 wherein J is        —CH₂(cyclopropyl) substituted with one cyano.    -   Embodiment 19k. A composition of Embodiment 19 wherein J is        cyclopropyl, unsubstituted or substituted with one cyano or one        C(O)NHR¹⁷.    -   Embodiments 20-20k are identical to Embodiments 19-19k except        that the ratio of the compound of Formula 1-1S to the compound        of Formula 1-1R is greater than 80:20.    -   Embodiments 21-21k are identical to Embodiments 19-19k except        that the ratio of the compound of Formula 1-1S to the compound        of Formula 1-1R is greater than 90:10.    -   Embodiments 22-22k are identical to Embodiments 19-19k except        that the ratio of the compound of Formula 1-1S to the compound        of Formula 1-1R is greater than 95:5.    -   Embodiments 23-23k are identical to Embodiments 19-19k except        that the ratio of the compound of Formula 1-1S to the compound        of Formula 1-1R is greater than 99:1.

Embodiments of this invention, including Embodiments 1-23k above as wellas any other embodiments described herein, can be combined in anymanner, and the descriptions of variables in the embodiments pertain notonly to the compounds of Formula 1 but also to the starting compoundsand intermediate compounds useful for preparing the compounds ofFormula 1. In addition, embodiments of this invention, includingEmbodiments 1-23k above as well as any other embodiments describedherein, and any combination thereof, pertain to the compositions andmethods of the present invention.

Combinations of Embodiments 1-23k are illustrated by:

-   -   Embodiment A. A compound of Formula 1 wherein J is J-1, J-2 or        J-5.    -   Embodiment B. The compound of Embodiment A wherein J is J-1.    -   Embodiment C. The compound of Embodiment B wherein R² is C₁-C₄        alkyl.    -   Embodiment D. The compound of Embodiment C wherein R² is methyl.    -   Embodiment E. The compound of Embodiment A wherein J is J-2.    -   Embodiment F. The compound of Embodiment E wherein R⁵ is H or        methyl.    -   Embodiment G. The compound of Embodiment F wherein Q is        pyridinyl or pyrimidinyl.    -   Embodiment H. The compound of any one of Embodiments E, F or G        wherein J-2 is

-   -   Embodiment I. The compound of Embodiment A wherein J is J-5.    -   Embodiment J. The compound of Embodiment I wherein R¹⁴ is C₁-C₄        alkyl.    -   Embodiment K. The compound of any one of Embodiments I or J        wherein J-5 is

-   -   Embodiment L. The compound of any one of Embodiments A-K wherein        the compound of Formula 1 is Formula 1-1S

-   -   Embodiment M. A compound of Formula 1 wherein J is C₂-C₄ alkyl        substituted with one cyano; —CH₂(cyclopropyl) substituted with        one cyano; or cyclopropyl, unsubstituted or substituted with one        cyano or one C(O)NHR¹⁷; or J-1, J-2 or J-5.    -   Embodiment N. A compound of Embodiment M wherein R^(1a) is Cl        and R^(1b) is Cl; or R^(1a) is CF₃ and R^(1b) is H.    -   Embodiment O. A compound of Embodiment N wherein J is C₂-C₄        alkyl substituted with one cyano; or cyclopropyl.    -   Embodiment P. A compound of Embodiment N wherein J is J-1.    -   Embodiment Q. A compound of Embodiment P wherein R² is methyl;    -   R³ is H or methyl; and    -   R⁴ is H or methyl.    -   Embodiment R. A compound of Embodiment N wherein J is J-2.    -   Embodiment 5. A compound of Embodiment R wherein R⁵ is H or        methyl; and    -   Q is pyridinyl or pyrimidinyl.    -   Embodiment T. A compound of Embodiment 5 wherein J-2 is

-   -   Embodiment U. A compound of Embodiment N wherein J is J-5.    -   Embodiment V. A compound of Embodiment U wherein R¹⁴ is H or        methyl; and    -   R¹⁵ is C₁-C₄ alkyl.    -   Embodiment W. A compound of Embodiment V wherein J-5 is

-   -   Embodiment L-1. The compound of Formula 1-1S

-   -   Embodiment L-2. A compound of Formula 1-1S wherein J is C₂-C₄        alkyl substituted with one cyano; —CH₂(cyclopropyl) substituted        with one cyano; or cyclopropyl, unsubstituted or substituted        with one cyano or one C(O)NHR¹⁷; or J-1, J-2 or J-5.    -   Embodiment L-3. A compound of Embodiment L-2 wherein R^(1a) is        Cl and R^(1b) is Cl; or R^(1a) is CF₃ and R^(1b) is H.    -   Embodiment L-4. A compound of Embodiment L-3 wherein J is C₂-C₄        alkyl substituted with one cyano; or cyclopropyl.    -   Embodiment L-5. A compound of Embodiment L-3 wherein J is J-1.    -   Embodiment L-6. A compound of Embodiment L-5 wherein R² is        methyl;    -   R³ is H or methyl; and    -   R⁴ is H or methyl.    -   Embodiment L-7. A compound of Embodiment L-3 wherein J is J-2.    -   Embodiment L-8. A compound of Embodiment L-7 wherein R⁵ is H or        methyl; and    -   Q is pyridinyl or pyrimidinyl.    -   Embodiment L-9. A compound of Embodiment L-8 wherein J-2 is

-   -   Embodiment L-10. A compound of Embodiment L-3 wherein J is J-5.    -   Embodiment L-11. A compound of Embodiment L-10 wherein R¹⁴ is H        or methyl; and    -   R¹⁵ is C₁-C₄ alkyl.    -   Embodiment L-12. A compound of Embodiment U wherein J-5 is

Specific embodiments include compounds of Formula 1 selected from thegroup consisting of compounds 1, 3, 8, 10, 11, 19, 20, 33, 34, 39, 50,61, 67, 69, 70 and 71. Compound numbers refer to the Index Tables.Specific embodiments thus include compounds of Formula 1 selected fromthe group consisting of a compound of Formula 1 wherein R^(1a) is Cl,R^(1b) is Cl, J is J-1, R² is methyl, R³ is H, and R⁴ is H (compound 1);a compound of Formula 1 wherein R^(1a) is Cl, R^(1b) is Cl, J is J-1, R²is methyl, R³ is H, and R⁴ is methyl (compound 3); a compound of Formula1 wherein R^(1a) is Cl, R^(1b) is Cl, J is J-2, R⁵ is H, and Q is2-pyrimidinyl (compound 10); a compound of Formula 1 wherein R^(1a) isCF₃, R^(1b) is Cl, J is J-2, R⁵ is H, and Q is 2-pyrimidinyl (compound11); a compound of Formula 1 wherein R^(1a) is Cl, R^(1b) is Cl, J isJ-2, R⁵ is methyl, and Q is 2-pyrimidinyl (compound 19); a compound ofFormula 1 wherein R^(1a) is Cl, R^(1b) is Cl, J is J-2a, R⁵ is methyl,and Q is 2-pyridinyl (compound 20); a compound of Formula 1 whereinR^(1a) is Cl, R^(1b) is Cl, J is J-3, R⁶ is H, and R⁷ is methyl(compound 33); a compound of Formula 1 wherein R^(1a) is Cl, R^(1b) isCl, J is J-4, X is 0, and R⁸ is ethyl (compound 34); a compound ofFormula 1 wherein R^(1a) is Cl, R^(1b) is Cl, J is J-5a, R¹⁴ is methyl,and R¹⁵ is methyl (compound 39); a compound of Formula 1 wherein R^(1a)is CF₃, R^(1b) is H, J is J-2, R⁵ is H, and Q is 2-pyrimidinyl (compound50); a compound of Formula 1 wherein R^(1a) is CF₃, R^(1b) is H, and Jis cyclopropyl (compound 67); a compound of Formula 1 wherein R^(1a) isCF₃, R^(1b) is H, and J is 1-(cyano)ethyl (compound 69); a compound ofFormula 1 wherein R^(1a) is Cl, R^(1b) is Cl, and J is cyclopropyl(compound 70); a compound of Formula 1 wherein R^(1a) is Cl, R^(1b) isCl, and J is 1-(cyano)ethyl (compound 71); a compound of Formula 1-1Swherein R^(1a) is Cl, R^(1b) is Cl, J is J-1, R² is methyl, R³ is H, andR⁴ is H (compound 8); and a compound of Formula 1-1S wherein R^(1a) isCl, R^(1b) is Cl, J is J-2, R⁵ is H, and Q is 2-pyrimidinyl (compound61).

Of note is that compounds of this invention are characterized byfavorable metabolic and/or soil residual patterns and exhibit activitycontrolling a spectrum of agronomic and nonagronomic invertebrate pests.

Of particular note, for reasons of invertebrate pest control spectrumand economic importance, protection of agronomic crops from damage orinjury caused by invertebrate pests by controlling invertebrate pestsare embodiments of the invention. Compounds of this invention because oftheir favorable translocation properties or systemicity in plants alsoprotect foliar or other plant parts which are not directly contactedwith a compound of Formula 1 or a composition comprising the compound.

Bioaccumulation of pesticides in non-target organisms is an importantsafety consideration and it is often desirable to limit the systemicexposure and/or accumulation of pesticides and/or their metabolites innon-target organisms. For example, if a compound is to be applied as aninsecticide to a crop plant, it is desirable that the compound does notaccumulate in the plasma or fat of a vertebrate animal.

Compounds of Formula 1 may show favorable pharmacokinetic properties invertebrate animals. In particular, compounds of Formula 1 have beenfound to have rapid clearance from vertebrate animal plasma/blood and alow distribution into vertebrate animal fat, thus reducing thepossibility of unwanted bioaccumulation. Of note is the fluorine atom atthe 4-position of the phenyl ring attached to the 5-position of theisoxazoline ring.

The pharmacokinetic properties of compounds of Formula 1 can be measuredusing a wide variety of assay protocols known in the science ofpharmacology. In one illustrative method involving a single oral dose,three male and three female rats each receive a single dose of a testsubstance via oral gavage. Blood is collected via tail vein at 0.25,0.5, 1, 2, 4, 8, 12 and 24 h, and then every 24 h thereafter untilsacrifice. To process the samples to plasma, blood is collected in tubescontaining ethylenediaminetetracetic acid (EDTA) and centrifuged atapproximately 3000 rpm to separate plasma from red blood cells.Alternatively, blood is collected using microcapillary tubes anddispensed into tubes containing HPLC water (1:1, v/v). Fat is alsocollected, homogenized and extracted to determine the concentration ofthe compound of Formula 1 at sacrifice. The plasma or blood and fat areanalyzed for the compound of Formula 1 and/or metabolites, for example,by high-performance liquid chromatography (HPLC) with tandem massspectrometry detection (LC/MS/MS) to determine the concentration of thetest substance. The plasma or blood pharmacokinetic data is analyzedusing nonlinear modeling software (e.g., Phoenix® WinNonlin®,Pharsight-A Certara™ Company, St. Louis, Mo., U.S.A.) to determine theplasma/blood half-life of the compound of Formula 1, the time afteradministration when the maximum plasma/blood concentration is reached(T_(max)), the maximum plasma/blood concentration (C_(max)), and thearea under the plasma/blood concentration curve (AUC). As analysis offat requires rat sacrifice, fat data is obtained at single time points(i.e. the time of rat sacrifice). The fat:plasma or fat:blood ratio ofthe compound of Formula 1 is then determined.

Also noteworthy as embodiments of the present invention are compositionscomprising a compound of any of the preceding Embodiments, as well asany other embodiments described herein, and any combinations thereof,and at least one additional component selected from the group consistingof a surfactant, a solid diluent and a liquid diluent, said compositionsoptionally further comprising at least one additional biologicallyactive compound or agent.

Further noteworthy as embodiments of the present invention arecompositions for controlling an invertebrate pest comprising a compoundof any of the preceding Embodiments, as well as any other embodimentsdescribed herein, and any combinations thereof, and at least oneadditional component selected from the group consisting of a surfactant,a solid diluent and a liquid diluent, said compositions optionallyfurther comprising at least one additional biologically active compoundor agent. Embodiments of the invention further include methods forcontrolling an invertebrate pest comprising contacting the invertebratepest or its environment with a biologically effective amount of acompound of any of the preceding Embodiments (e.g., as a compositiondescribed herein).

Embodiments of the invention also include a composition comprising acompound of any of the preceding Embodiments, in the form of a soildrench liquid formulation. Embodiments of the invention further includemethods for controlling an invertebrate pest comprising contacting thesoil with a liquid composition as a soil drench comprising abiologically effective amount of a compound of any of the precedingEmbodiments.

Embodiments of the invention also include a spray composition forcontrolling an invertebrate pest comprising a biologically effectiveamount of a compound of any of the preceding Embodiments and apropellant. Embodiments of the invention further include a baitcomposition for controlling an invertebrate pest comprising abiologically effective amount of a compound of any of the precedingEmbodiments, one or more food materials, optionally an attractant, andoptionally a humectant. Embodiments of the invention also include adevice for controlling an invertebrate pest comprising said baitcomposition and a housing adapted to receive said bait composition,wherein the housing has at least one opening sized to permit theinvertebrate pest to pass through the opening so the invertebrate pestcan gain access to said bait composition from a location outside thehousing, and wherein the housing is further adapted to be placed in ornear a locus of potential or known activity for the invertebrate pest.

Embodiments of the invention also include methods for protecting a seedfrom an invertebrate pest comprising contacting the seed with abiologically effective amount of a compound of any of the precedingEmbodiments.

Embodiments of the invention also include methods for controlling aninvertebrate pest comprising contacting the invertebrate pest or itsenvironment with a biologically effective amount of a compound ofFormula 1 (e.g., as a composition described herein), provided that themethods are not methods of medical treatment of a human body by therapy.

This invention also relates to such methods wherein the invertebratepest or its environment is contacted with a composition comprising abiologically effective amount of a compound of Formula 1, and at leastone additional component selected from the group consisting ofsurfactants, solid diluents and liquid diluents, said compositionoptionally further comprising a biologically effective amount of atleast one additional biologically active compound or agent, providedthat the methods are not methods of medical treatment of a human body bytherapy.

The compounds of Formula 1 can be prepared by one or more of thefollowing methods and variations as described in Schemes 1-11. Thedefinitions of substituents in the compounds of Formulae 1-15 below areas defined above in the Summary of the Invention unless otherwise noted.Compounds of Formulae 1a and 1b are subsets of the compounds of Formula1, and all substituents for Formulae 1a and 1b are as defined above forFormula 1. The following abbreviations may be used: DMF isN,N-dimethylformamide, and DBU is 1,8-diazabicyclo[5.4.0]undec-7-ene.

Compounds of Formula 1a (Formula 1 wherein J is J-1, J-2, J-4, J-5 orJ-6) can be prepared from compounds of Formula 2 by the method shown inScheme 1. In this method, a carboxylic acid of Formula 2 is coupled withan amine compound of Formula of 3 (wherein J is J-1, J-2, J-4, J-5 orJ-6), generally in the presence of a dehydrating coupling reagent.Coupling reagents useful in this method include dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and carbonyldiimidazole. Further coupling reagents useful in this method include1-propanephosphonic acid cyclic anhydride,1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium3-oxide hexafluorophosphate andN-[dimethylamino)-1H-1,2,3-triazolo-[4,5-b]pyridin-1-ylmethylene]-N-methylmethanaminiumhexafluorophosphate N-oxide; these coupling reagents are generally usedin the presence of a base such as triethylamine, pyridine,4-(dimethylamino)pyridine or N,N-diisopropylethylamine. Typical reactionconditions include an anhydrous aprotic solvent such as dichloromethane,tetrahydrofuran or DMF, and a reaction temperature between roomtemperature and 70° C.

The compounds of Formula of 1a can also be prepared by converting thecarboxylic acids of Formula of 2 to their corresponding acid chlorides,and then coupling the acid chlorides with the amines of Formula of 3.The method of Scheme 1 is illustrated in Step C of Synthesis Example 1,and in Synthesis Examples 2 and 4.

Compounds of Formula 1a (Formula 1 wherein J is J-1, J-2, J-4, J-5 orJ-6) can also be prepared by the method shown in Scheme 2. In thismethod, an aryl bromide or iodide of Formula 4 is carbonylated andcoupled with an amine compound of Formula of 3 (wherein J is J-1, J-2,J-4, J-5 or J-6).

This aminocarbonylation method typically involves treatment of an arylbromide of Formula 4 (wherein X is Br or I) with an amine of Formula 3in the presence of a palladium catalyst under a CO (carbon monoxide)atmosphere. Palladium catalysts useful in this method typically comprisepalladium in a formal oxidation state of either 0 (i.e. Pd(0)) or 2(i.e. Pd(II)). Examples of palladium-containing compounds and complexesuseful as catalysts in this method include PdCl₂(PPh₃)₂(bis(triphenylphosphine)palladium (II) dichloride), Pd(PPh₃)₄(tetrakis(triphenylphosphine)palladium(O)), Pd(C₅H₇O₂)₂ (palladium(II)acetylacetonate), Pd₂(dba)₃ (tris(dibenzylideneacetone)dipalladium(0)),and [1,1′-bis(diphenylphosphino)-ferrocene]dichloropalladium(II). Themethod of Scheme 2 is generally conducted in a liquid phase, with thepalladium catalyst having good solubility in the liquid phase. Usefulliquid phase solvents include ethers such as 1,2-dimethoxyethane, amidessuch as N,N-dimethyl-acetamide, and non-halogenated aromatichydrocarbons such as toluene.

The method of Scheme 2 can be conducted over a wide range oftemperatures, ranging from about 25 to about 150° C. Of note aretemperatures from about 60 and about 110° C., which typically providefaster reaction rates and higher product yields. Literature examples ofaminocarbonylation methods include H. Horino et al., Synthesis 1989,715; and J. J. Li, G. W. Gribble, editors, Palladium in HeterocyclicChemistry: A Guide for the Synthetic Chemist, 2000. The method of Scheme2 is illustrated in Step B of Synthesis Example 5.

Compounds of Formula 1 wherein J is (i) C₂-C₄ alkyl substituted with onecyano, (ii) —CH₂(cyclopropyl) substituted with one cyano, or (iii)cyclopropyl, unsubstituted or substituted with one cyano or oneC(O)NHR¹⁷, can be prepared by methods similar to the methods describedin Schemes 1 and 2.

Compounds of Formula 1b (Formula 1 wherein J is J-3) can be preparedfrom compounds of Formula 5 by the method shown in Scheme 3. In thismethod, an amide of Formula 5 is treated with an appropriatelysubstituted amine of Formula 6.

The method of Scheme 3 can be performed by treatment of the amide ofFormula 5 with DMF-DMA at a temperature ranging from about 25 to about110° C., followed by coupling with the amine of Formula of 6 or itscorresponding salt. The compounds of Formula 1b can also be prepared byin a single step by treatment of the amide of Formula 5 with triethylorthoformate and the amine of Formula of 6 or its corresponding salt intoluene. For literature examples of this method, see T. Mita et al., WO2009/005015; W. Zhao et al., Org. Lett. 2011, 5160; and Y. Kusuoka etal., WO 2014/126208. The method of Scheme 3 is illustrated in Step B ofSynthesis Example 3.

Compounds of Formula 5 can be prepared from the corresponding carboxylicacids of Formula 2 as shown in the method of Scheme 4.

The general transformation shown in Scheme 4 is well-known in theliterature, and includes the coupling of carboxylic acids with ammoniasources such as ammonium hydroxide, ammonium in dioxane, and ammoniumcarbonate, via their corresponding acid chlorides. Alternatively, thecoupling can be performed directly in the presence of coupling reagentssuch as HBTU in solvents such as THF or dioxanes. The method of Scheme 4is illustrated in Step A of Synthesis Example 3.

Compounds of Formula 2 can be prepared by hydrolysis of esters ofFormula 7 (wherein Ra is methyl or ethyl) as shown in the method ofScheme 5.

In this method, the ester of Formula 7 is converted to the correspondingcarboxylic acid of Formula 2 by procedures known in the art. Forexample, treatment of the ester of Formula 7 with aqueous lithiumhydroxide in tetrahydrofuran, followed by acidification, yields thecorresponding carboxylic acid of Formula 2. The method of Scheme 5 isillustrated in Step B of Synthesis Example 1.

Compounds of Formula 7 can be prepared by the 1,3-dipolar cycloadditionof styrenes of Formula 8 with nitrile oxides derived from oximes ofFormula 9 as shown in the method of Scheme 6.

This method typically involves chlorination of the oxime of Formula 9and subsequent dehydrochlorination to yield an in situ generated nitrileoxide, which then undergoes 1,3-dipolar cycloaddition with the styreneof Formula 8 to afford the compound of Formula 7. In a typicalprocedure, a chlorinating reagent such as sodium hypochlorite,N-chlorosuccinimide, or chloramine-T is combined with the oxime ofFormula 9 in the presence of the styrene of Formula 8. Depending on thereaction conditions, an amine base such as pyridine or triethylamine maybe necessary to facilitate the dehydrochlorination reaction. Solventsuseful in this method include tetrahydrofuran, diethyl ether, methylenechloride, dioxane, and toluene. Reaction temperatures range from roomtemperature to the reflux temperature of the solvent. For generalprocedures for the cycloaddition of nitrile oxides and olefins, see Lee,Synthesis, 1982, 6, 508-509; Kanemasa et al., Tetrahedron, 2000, 56,1057-1064; EP 1,538,138 A1, as well as references cited within. Themethod of Scheme 6 is illustrated in Step A of Synthesis Example 1.

Compounds of Formulae 8 and 9 are commercially available or are known inthe art; see, for example, T. Mita et al., U.S. Pat. No. 7,951,828, andG. Lahm et al., WO 2007/079162.

Compounds of Formula 4 can be prepared by the 1,3-dipolar cycloadditionof styrenes of Formula 8 with nitrile oxides derived from oximes ofFormula 10 as shown in the method of Scheme 7.

The method of Scheme 7 is similar to the method of Scheme 6. The oximesof Formula 10 are commercially available or are known in the art; see,for example, G. Lahm et al., WO 2007/079162. The method of Scheme 7 isillustrated in Step A of Synthesis Example 5.

Compounds of Formula 7 can also be prepared by the cyclization ofcompounds of Formula 11 with hydroxylamine as shown in the method ofScheme 8.

In this method, isoxazolines of Formula 7 can be formed by treatment ofketones of Formula of 11 with hydroxylamine or its salt in the presenceof an aqueous base such as NaOH, Cs₂CO₃ or K₂CO₃, in a solvent such asdichloroethane, chloroform or THF. For examples of this method, see G.Annis, WO 2009/126668; and K. Matoba et al., Angew. Chem. Int. Ed. 2010,49(33), 5762.

Compounds of Formula 11 can be prepared by the condensation of compoundsof Formula 12 with naphthalene ketones of Formula 13 as shown in themethod of Scheme 9.

This method involves reaction of the compounds of Formulae 12 and 13 inthe presence of a base such as Ca(OH)₂, K₂CO₃, CsCO₃ in a solvent suchas toluene, DMF, MTBE, trifluormethylbenzene or acetonitrile, or in amixture of such solvents. Typical reaction temperatures range from about60 to about 130° C. For an example of this method, see G. Annis, WO2009/126668.

Compounds of Formulae 12 and 13 are commercially available or are knownin the art; see, for example, Chunhua Yang et al., WO 2017/176948; D.Leysen et al., WO 2005/082236; and F. Cohen et al., WO 2006/069063.

Compounds of Formula 4 can also be prepared by the cyclization ofcompounds of Formula 14 with hydroxylamine as shown in the method ofScheme 10.

This method is similar to the method described in Scheme 8. Analogoustreatment of the compounds of Formula 14 with hydroxylamine formsisoxazolines of Formula 4.

Compounds of Formula 14 can be prepared by the condensation of compoundsof Formula 12 and naphthalene ketones of Formula 15 as shown in themethod of Scheme 11.

This method is similar to the method described in Scheme 9. Analogoustreatment of the compounds of Formula 12 and the naphthalene ketones ofFormula 15 with base forms the compounds of Formula 14. Compounds ofFormulae 12 and 15 are commercially available or are known in the art;see, for example, D. Leysen et al., WO 2005/082236; and F. Cohen et al.,WO 2006/069063.

It is recognized that some reagents and reaction conditions describedabove for preparing compounds of Formula 1 may not be compatible withcertain functionalities present in the intermediates. In theseinstances, the incorporation of protection/deprotection sequences orfunctional group interconversions into the synthesis will aid inobtaining the desired products.

The use and choice of the protecting groups will be apparent to oneskilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P.G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York,1991). One skilled in the art will recognize that, in some cases, afterintroduction of the reagents depicted in the individual schemes,additional routine synthetic steps not described in detail may be neededto complete the synthesis of compounds of Formula 1. One skilled in theart will also recognize that it may be necessary to perform acombination of the steps illustrated in the above schemes in an orderother than that implied by the particular sequence presented to preparethe compounds of Formula 1.

One skilled in the art will also recognize that compounds of Formula 1and the intermediates described herein can be subjected to variouselectrophilic, nucleophilic, radical, organometallic, oxidation, andreduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the artusing the preceding description can utilize the present invention to itsfullest extent. The following Synthesis Examples are, therefore, to beconstrued as merely illustrative, and not limiting of the disclosure inany way whatsoever. Steps in the following Synthesis Examples illustratea procedure for each step in an overall synthetic transformation, andthe starting material for each step may not have necessarily beenprepared by a particular preparative run whose procedure is described inother Examples or Steps. Percentages are by weight except forchromatographic solvent mixtures or where otherwise indicated. Parts andpercentages for chromatographic solvent mixtures are by volume unlessotherwise indicated. ¹H NMR spectra are reported in ppm downfield fromtetramethylsilane; “s” means singlet, “d” means doublet, “t” meanstriplet, “q” means quartet, “m” means multiplet, “dd” means doublet ofdoublets, “dt” means doublet of triplets, “br s” means broad singlet.DMF means N,N-dimethylformamide Compound numbers refer to Index TablesA-G.

Synthesis Example 1 Preparation ofN-[(1R)-2-amino-1-methyl-2-oxoethyl]-4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxamide(compound 1) Step A: Preparation of methyl4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxylate

To a stirred solution of methyl4-[(hydroxyimino)methyl]-1-naphthalenecarboxylate (1.50 g, 6.55 mmol) inN,N-dimethylformamide (4.0 mL) was added N-chlorosuccinimide (1.05 g,7.86 mmol). This mixture was stirred for 1.5 h at room temperature, andthen a solution of1,3-dichloro-4-fluoro-5-[1-(trifluoromethyl)ethenyl]benzene (2.04 g,7.86 mmol) and triethylamine (1.38 mL, 9.83 mmol) inN,N-dimethylformamide (10.0 mL) was added. After stirring for additional2 h at room temperature, the reaction mixture was diluted with water andextracted with ethyl acetate. The organic layer was washed with brine,dried (Na₂SO₄), and concentrated under reduced pressure. The residue waspurified by silica gel chromatography using hexanes/ethyl acetate aseluent to afford the title compound as a white solid (1.30 g, 43%yield). ¹H NMR (CDCl₃): 8.87 (m, 1H), 8.78 (m, 1H), 8.08 (d, 1H), 7.67(m, 2H), 7.63 (d, 2H), 7.52 (d, 1H), 4.27 (d, 1H), 4.02 (s, 3H), 3.89(d, 1H).

Step B: Preparation of4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxylicacid

To a stirred solution of methyl4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxylate(i.e. the product from Step A) (1.20 g, 2.47 mmol) in tetrahydrofuran(10 mL) was added a solution of lithium hydroxide monohydrate (0.31 g,7.41 mmol) in water (10 mL). The resulting mixture was stirred overnightat room temperature. The reaction mixture was partitioned between waterand diethyl ether. Then the aqueous layer was acidified with 6 N aqueoushydrochloric acid to pH 2 and extracted with ethyl acetate. The combinedorganic layers were washed with brine, dried and concentrated to providethe title compound as a white solid (1.10 g, 94% yield).

¹H NMR (DMSO-d₆): 13.52 (br s, 1H), 8.83 (m, 1H), 8.77 (m, 1H), 8.12 (d,1H), 7.92 (d, 1H), 7.88 (d, 2H), 7.73 (m, 2H), 4.56 (s, 2H).

Step C: Preparation ofN-[(1R)-2-amino-1-methyl-2-oxoethyl]-4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxamide

A mixture of4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxylicacid (i.e. the product from Step B) (190 mg, 0.40 mmol),(R)-2-aminopropanamide hydrochloride (97 mg, 0.80 mmol), triethylamine(0.17 mL, 1.20 mmol) and1-[bis(dimethylamino)methylene-1H-1,2,3-triazolo[4,5-b]pyridinium3-oxide hexafluorophosphate (HATU, 182 mg, 0.48 mmol) in DMF (3 mL) wasstirred at room temperature overnight. The reaction mixture was thenpartitioned between ethyl acetate and water, the phases were separated,and the aqueous phase was extracted with ethyl acetate. The combinedorganic layers were washed with brine, dried, and concentrated. Theresulting residue was purified by column chromatography on silica gelusing hexanes/ethyl acetate as eluent to give the title product, acompound of the present invention, as a white solid (180 mg, 83% yield).¹H NMR (DMSO-d₆): 8.77 (d, 1H), 8.72 (d, 1H), 8.30 (d, 1H), 7.88 (m,3H), 7.63-7.72 (m, 3H), 7.46 (br s, 1H), 7.05 (br s, 1H), 4.54 (s, 2H),4.50 (m, 1H), 1.36 (d, 3H).

Synthesis Example 2 Preparation of4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-(2-pyridinylmethyl)-1-naphthalenecarboxamide(compound 15)

A mixture of4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxylicacid (200 mg, 0.42 mmol), 2-pyridylmethanamine (92 mg, 0.84 mmol),triethylamine (0.18 mL, 1.26 mmol) and1-[bis(dimethylamino)methylene-1H-1,2,3-triazolo[4,5-b]pyridinium3-oxide hexafluorophosphate (HATU, 240 mg, 0.64 mmol) in DMF (3 mL) wasstirred at room temperature overnight. The reaction mixture was thenpartitioned between ethyl acetate and water. The phases were separated,and the aqueous phase was extracted with ethyl acetate. The combinedorganic layers were washed with brine, dried, and concentrated. Theresulting residue was purified by column chromatography on silica gelusing hexanes/ethyl acetate as eluent to give the title product, acompound of the present invention, as a white solid (132 mg, 56% yield).¹H NMR (CDCl₃): 8.80 (d, 1H), 8.50 (d, 1H), 8.36 (d, 1H), 7.71 (ddd,1H), 7.58-7.66 (m, 5H), 7.49 (s, 1H), 7.48 (s, 1H), 7.36 (d, 1H), 7.22(dd, 1H), 4.84 (d, 2H), 4.25 (d, 1H), 3.89 (d, 1H).

Synthesis Example 3 Preparation of4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[(methoxyimino)methyl]-1-naphthalenecarboxamide(compound 33) Step A: Preparation of4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxamide

To a suspension of4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxylicacid (500 mg, 1.06 mmol) in dichloromethane (20 mL) was added oxalylchloride (269 mg, 2.12 mmol) and 1 drop of DMF. The mixture was stirredat room temperature for 1 hr, then concentrated and distilled withtoluene under reduced pressure. The residue was dissolved in THF (5 mL)and ammonium hydroxide aqueous solution (3 mL, 14.8 M) was added. Thereaction mixture was stirred at room temperature for 4 hr, and thenpartitioned between ethyl acetate and water. The layers were separated,and the aqueous layer was extracted with ethyl acetate. The combinedorganic layers were washed with brine, dried, and concentrated to givethe primary amide as a white solid (490 mg). The crude amide was useddirectly in the next step without further purification.

Step B: Preparation of4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-[(methoxyimino)methyl]-1-naphthalenecarboxamide

A mixture of the4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxamide(490 mg), methoxyamine hydrochloride (266 mg, 3.18 mmol), and triethylorthoformate (2 mL, 12 mmol) in toluene (20 mL) was stirred at 70° C.for 24 hr. The reaction mixture was cooled and partitioned between ethylacetate and water. The layers were separated, and the aqueous layer wasextracted with ethyl acetate. The combined organic layers were washedwith brine, dried, concentrated, and the residue was purified by columnchromatography on silica gel using hexanes/ethyl acetate as eluent togive the title product, a compound of the present invention, as a whitesolid (402 mg, 72% yield in two steps). ¹H NMR (CDCl₃): 8.83 (d, 1H),8.66 (d, 1H), 8.34 (d, 1H), 7.89 (d, 1H), 7.69 (m, 3H), 7.64 (d, 2H),7.54 (d, 1H), 4.27 (d, 1H), 3.90 (d, 1H), 3.89 (s, 3H).

Synthesis Example 4 Preparation of4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-N-(2-pyridinylmethyl)-N-[(4R)-2-ethyl-3-oxo-4-isoazolidinyl]-1-naphthalenecarboxamide(compound 34)

To a suspension of4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenecarboxylicacid (200 mg, 0.42 mmol) in dichloromethane (10 mL) was added oxalylchloride (107 mg, 0.84 mmol) and 1 drop of DMF. The mixture was stirredat room temperature for 1 hr, then concentrated and distilled withtoluene under reduced pressure. The residue was dissolved in 2 mL ofdichloromethane and added slowly to a suspension of(4R)-4-amino-2-ethylisoxazolidin-3-one hydrochloride (210 mg, 1.26 mmol)and triethylamine (170 mg, 1.68 mmor) in dichloromethane (5 mL) at roomtemperature. The reaction mixture was stirred at room temperatureovernight, then concentrated, and the residue purified by silica gelcolumn chromatography using hexanes/ethyl acetate as eluent to affordthe title compound as a white solid (196 mg, 79% yield). ¹H NMR (CDCl₃):8.81 (d, 1H), 8.30 (d, 1H), 7.60-7.67 (m, 5H), 7.45 (d, 1H), 6.85 (br s,1H), 5.00 (m, 2H), 4.26 (d, 1H), 4.13 (dd, 1H), 3.89 (d, 1H), 3.65 (m,2H), 1.26 (t, 3H).

Synthesis Example 5 Preparation ofN-[[4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenyl]carbonyl]glycinemethyl ester (compound 35) Step A: Preparation of3-(4-bromo-1-naphthalenyl)-5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)isoxazole

To a stirred solution of 4-bromo-1-naphthalenecarboxylate oxime (1.00 g,4.0 mmol) in N,N-dimethylformamide (12.0 mL) was addedN-chlorosuccinimide (0.64 g, 4.8 mmol). The reaction mixture was stirredfor 1 h at room temperature, and then a solution of 1,3-dichloro,4-fluoro-5-[1-(trifluoromethyl)ethenyl]benzene (1.24 g, 4.8 mmol) andtriethylamine (1.68 mL, 12.0 mmol) in N,N-dimethylformamide (12.0 mL)was added. After stirring for additional 2 h at room temperature, thereaction mixture was diluted with water and extracted with ethylacetate. The organic layer was washed with brine, dried (Na₂SO₄), andconcentrated under reduced pressure. The residue was purified by silicagel column chromatography using hexanes/ethyl acetate as eluent toafford the title compound as a white solid (1.60 g, 76% yield). ¹H NMR(CDCl₃): 8.88 (m, 1H), 8.35 (m, 1H), 7.82 (d, 1H), 7.69 (m, 2H), 7.64(d, 2H), 7.36 (d, 1H), 4.27 (d, 1H), 3.88 (d, 1H).

Step B: Preparation ofN-[[4-[5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-1-naphthalenyl]carbonyl]glycinemethyl ester

A mixture of3-(4-bromo-1-naphthalenyl)-5-(3,5-dichloro-4-fluorophenyl)-4,5-dihydro-5-(trifluoromethyl)isoxazole(1000 mg, 1.97 mmol),[1,1′-bis(diphenylphosphino)-ferrocene]dichloropalladium(II)(PdCl₂(dppf)) (146 mg, 0.20 mmol), glycine methyl ester hydrochloride(371 mg, 2.96 mmol) and triethylamine (2.76 mL, 19.7 mmol) in toluene(20 mL) was purged with carbon monoxide for 15 minutes. The reactionmixture was stirred at 70° C. under a carbon monoxide atmosphereovernight. The mixture was cooled to room temperature, filtered througha short pad of Celite® diatomaceous filter aid, and rinsed with a smallamount of ethyl acetate. The filtrate was concentrated, and the residuewas purified by column chromatography on silica gel using hexanes/ethylacetate as eluent to provide the title product, a compound of thepresent invention, as a white solid (600 mg, 56% yield). ¹H NMR(DMSO-d₆): 9.13 (t, 1H), 8.78 (d, 1H), 8.32 (d, 1H), 7.90 (m, 3H), 7.70(m, 3H), 4.53 (s, 2H), 4.11 (d, 2H), 4.74 (s, 3H).

Synthesis Example 1 above is an example of the preparation of a compoundof Formula 1 wherein J is J-1.

Synthesis Example 2 above is an example of the preparation of a compoundof Formula 1 wherein J is J-2.

Synthesis Example 3 above is an example of the preparation of a compoundof Formula 1 wherein J is J-3.

Synthesis Example 4 above is an example of the preparation of a compoundof Formula 1 wherein J is J-4.

Synthesis Example 5 above is an example of the preparation of a compoundof Formula 1 wherein J is J-5.

Compounds of Formula 1 wherein J is J-6 can be prepared by proceduressimilar to those described above in Synthesis Examples 1, 2, 4 and 5.

Compounds of Formula 1 wherein J is (i) C₂-C₄ alkyl substituted with onecyano, (ii) —CH₂(cyclopropyl) substituted with one cyano, or (iii)cyclopropyl, unsubstituted or substituted with one cyano or oneC(O)NHR¹⁷, can be prepared by procedures similar to those describedabove in Synthesis Examples 1, 2, 4 and 5.

By the procedures described herein together with methods known in theart, the following compounds of Tables 1-1 to 7-2 can be prepared. Thefollowing abbreviations are used in the Tables which follow: Me meansmethyl, Et means ethyl, i-Pr means isopropyl, i-Bu means isobutyl, andOMe means methoxy.

TABLE 1-1

R^(1a) R^(1b) R² R³ R⁴ Cl Cl Me H H Cl Cl Cl H Me Cl Cl Me H Et Cl Cl MeH i-Pr Cl Cl Me H CH₂CF₃ Cl Cl Me Me H Cl Cl Me Me Me Cl Cl Me Me Et ClCl Me Me i-Pr Cl Cl Me Me CH₂CF₃ Cl Cl Et H H Cl Cl Et H Me Cl Cl Et HEt Cl Cl Et H i-Pr Cl Cl Et H CH₂CF₃ Cl Cl Et Me H Cl Cl Et Me Me Cl ClEt Me Et Cl Cl Et Me i-Pr Cl Cl Et Me CH₂CF₃ Cl Cl i-Pr H H Cl Cl i-Pr HMe Cl Cl i-Pr H Et Cl Cl i-Pr H i-Pr Cl Cl i-Pr H CH₂CF₃ Cl Cl i-Pr Me HCl Cl i-Pr Me Me Cl Cl i-Pr Me Et Cl Cl i-Pr Me i-Pr Cl Cl i-Pr MeCH₂CF₃ Cl Cl i-Bu H H Cl Cl i-Bu H Me Cl Cl i-Bu H Et Cl Cl i-Bu H i-PrCl Cl i-Bu H CH₂CF₃ Cl Cl i-Bu Me H Cl Cl i-Bu Me Me Cl Cl i-Bu Me Et ClCl i-Bu Me i-Pr Cl Cl i-Bu Me CH₂CF₃ Cl Cl CH₂OH H H Cl Cl CH₂OH H Me ClCl CH₂OH H Et Cl Cl CH₂OH H i-Pr Cl Cl CH₂OH H CH₂CF₃ Cl Cl CH₂OH Me HCl Cl CH₂OH Me Me Cl Cl CH₂OH Me Et Cl Cl CH₂OH Me i-Pr Cl Cl CH₂OH MeCH₂CF₃ Cl Cl CH₂OMe H H Cl Cl CH₂OMe H Me Cl Cl CH₂OMe H Et Cl Cl CH₂OMeH i-Pr Cl Cl CH₂OMe H CH₂CF₃ Cl Cl CH₂OMe Me H Cl Cl CH₂OMe Me Me Cl ClCH₂OMe Me Et Cl Cl CH₂OMe Me i-Pr Cl Cl CH₂OMe Me CH₂CF₃ CF₃ Cl Me H HCF₃ Cl Me H Me CF₃ Cl Me H Et CF₃ Cl Me H i-Pr CF₃ Cl Me H CH₂CF₃ CF₃ ClMe Me H CF3 Cl Me Me Me CF₃ Cl Me Me Et CF₃ Cl Me Me i-Pr CF₃ Cl Me MeCH₂CF₃ CF₃ Cl Et H H CF₃ Cl Et H Me CF₃ Cl Et H Et CF₃ Cl Et H i-Pr CF₃Cl Et H CH₂CF₃ CF₃ Cl Et Me H CF₃ Cl Et Me Me CF₃ Cl Et Me Et CF₃ Cl EtMe i-Pr CF₃ Cl Et Me CH₂CF₃ CF₃ Cl i-Pr H H CF₃ Cl i-Pr H Me CF₃ Cl i-PrH Et CF₃ Cl i-Pr H i-Pr CF₃ Cl i-Pr H CH₂CF₃ CF₃ Cl i-Pr Me H CF₃ Cli-Pr Me Me CF₃ Cl i-Pr Me Et CF₃ Cl i-Pr Me i-Pr CF₃ Cl i-Pr Me CH₂CF₃CF₃ H Me H H CF₃ H Me H Me CF₃ H Me H Et CF₃ H Me H i-Pr CF₃ H Me HCH₂CF₃ CF₃ H Me Me H CF₃ H Me Me Me CF₃ H Me Me Et CF₃ H Me Me i-Pr CF₃H Me Me CH₂CF₃ CF₃ H Et H H CF₃ H Et H Me CF₃ H Et H Et CF₃ H Et H i-PrCF₃ H Et H CH₂CF₃ CF₃ H Et Me H CF₃ H Et Me Me CF₃ H Et Me Et CF₃ H EtMe i-Pr CF₃ H Et Me CH₂CF₃ CF₃ H i-Pr H H CF₃ H i-Pr H Me CF₃ H i-Pr HEt CF₃ H i-Pr H i-Pr CF₃ H i-Pr H CH₂CF₃ CF₃ H i-Pr Me H CF₃ H i-Pr MeMe CF₃ H i-Pr Me Et CF₃ H i-Pr Me i-Pr CF₃ H i-Pr Me CH₂CF₃ CF₃ H i-Bu HH CF₃ H i-Bu H Me CF₃ H i-Bu H Et CF₃ H i-Bu H i-Pr CF₃ H i-Bu H CH₂CF₃CF₃ H i-Bu Me H CF₃ H i-Bu Me Me CF₃ H i-Bu Me Et CF₃ H i-Bu Me i-Pr CF₃H i-Bu Me CH₂CF₃ CF₃ H CH₂OH H H CF₃ H CH₂OH H Me CF₃ H CH₂OH H Et CF₃ HCH₂OH H i-Pr CF₃ H CH₂OH H CH₂CF₃ CF₃ H CH₂OH Me H CF₃ H CH₂OH Me Me CF₃H CH₂OH Me Et CF₃ H CH₂OH Me i-Pr CF₃ H CH₂OH Me CH₂CF₃ CF₃ H CH₂OMe H HCF₃ H CH₂OMe H Me CF₃ H CH₂OMe H Et CF₃ H CH₂OMe H i-Pr CF₃ H CH₂OMe HCH₂CF₃ CF₃ H CH₂OMe Me H CF₃ H CH₂OMe Me Me CF₃ H CH₂OMe Me Et CF₃ HCH₂OMe Me i-Pr CF₃ H CH₂OMe Me CH₂CF₃ CF₃ Cl i-Bu H H CF₃ Cl i-Bu H MeCF₃ Cl i-Bu H Et CF₃ Cl i-Bu H i-Pr CF₃ Cl i-Bu H CH₂CF₃ CF₃ Cl i-Bu MeH CF₃ Cl i-Bu Me Me CF₃ Cl i-Bu Me Et CF₃ Cl i-Bu Me i-Pr CF₃ Cl i-Bu MeCH₂CF₃ CF₃ Cl CH₂OH H H CF₃ Cl CH₂OH H Me CF₃ Cl CH₂OH H Et CF₃ Cl CH₂OHH i-Pr CF₃ Cl CH₂OH H CH₂CF₃ CF₃ Cl CH₂OH Me H CF₃ Cl CH₂OH Me Me CF₃ ClCH₂OH Me Et CF₃ Cl CH₂OH Me i-Pr CF₃ Cl CH₂OH Me CH₂CF₃ CF₃ Cl CH₂OMe HH CF₃ Cl CH₂OMe H Me CF₃ Cl CH₂OMe H Et CF₃ Cl CH₂OMe H i-Pr CF₃ ClCH₂OMe H CH₂CF₃ CF₃ Cl CH₂OMe Me H CF₃ Cl CH₂OMe Me Me CF₃ Cl CH₂OMe MeEt CF₃ Cl CH₂OMe Me i-Pr CF₃ Cl CH₂OMe Me CH₂CF₃

TABLE 1-2

R^(1a) R^(1b) R² R³ R⁴ Cl Cl Me H H Cl Cl Cl H Me Cl Cl Me H Et Cl Cl MeH i-Pr Cl Cl Me H CH₂CF₃ Cl Cl Me Me H Cl Cl Me Me Me Cl Cl Me Me Et ClCl Me Me i-Pr Cl Cl Me Me CH₂CF₃ Cl Cl Et H H Cl Cl Et H Me Cl Cl Et HEt Cl Cl Et H i-Pr Cl Cl Et H CH₂CF₃ Cl Cl Et Me H Cl Cl Et Me Me Cl ClEt Me Et Cl Cl Et Me i-Pr Cl Cl Et Me CH₂CF₃ Cl Cl i-Pr H H Cl Cl i-Pr HMe Cl Cl i-Pr H Et Cl Cl i-Pr H i-Pr Cl Cl i-Pr H CH₂CF₃ Cl Cl i-Pr Me HCl Cl i-Pr Me Me Cl Cl i-Pr Me Et Cl Cl i-Pr Me i-Pr Cl Cl i-Pr MeCH₂CF₃ Cl Cl i-Bu H H Cl Cl i-Bu H Me Cl Cl i-Bu H Et Cl Cl i-Bu H i-PrCl Cl i-Bu H CH₂CF₃ Cl Cl i-Bu Me H Cl Cl i-Bu Me Me Cl Cl i-Bu Me Et ClCl i-Bu Me i-Pr Cl Cl i-Bu Me CH₂CF₃ Cl Cl CH₂OH H H Cl Cl CH₂OH H Me ClCl CH₂OH H Et Cl Cl CH₂OH H i-Pr Cl Cl CH₂OH H CH₂CF₃ Cl Cl CH₂OH Me HCl Cl CH₂OH Me Me Cl Cl CH₂OH Me Et Cl Cl CH₂OH Me i-Pr Cl Cl CH₂OH MeCH₂CF₃ Cl Cl CH₂OMe H H Cl Cl CH₂OMe H Me Cl Cl CH₂OMe H Et Cl Cl CH₂OMeH i-Pr Cl Cl CH₂OMe H CH₂CF₃ Cl Cl CH₂OMe Me H Cl Cl CH₂OMe Me Me Cl ClCH₂OMe Me Et Cl Cl CH₂OMe Me i-Pr Cl Cl CH₂OMe Me CH₂CF₃ CF₃ Cl Me H HCF₃ Cl Me H Me CF₃ Cl Me H Et CF₃ Cl Me H i-Pr CF₃ Cl Me H CH₂CF₃ CF₃ ClMe Me H CF₃ Cl Me Me Me CF₃ Cl Me Me Et CF₃ Cl Me Me i-Pr CF₃ Cl Me MeCH₂CF₃ CF₃ Cl Et H H CF₃ Cl Et H Me CF₃ Cl Et H Et CF₃ Cl Et H i-Pr CF₃Cl Et H CH₂CF₃ CF₃ Cl Et Me H CF₃ Cl Et Me Me CF₃ Cl Et Me Et CF₃ Cl EtMe i-Pr CF₃ Cl Et Me CH₂CF₃ CF₃ Cl i-Pr H H CF₃ Cl i-Pr H Me CF₃ Cl i-PrH Et CF₃ Cl i-Pr H i-Pr CF₃ Cl i-Pr H CH₂CF₃ CF₃ Cl i-Pr Me H CF₃ Cli-Pr Me Me CF₃ Cl i-Pr Me Et CF₃ Cl i-Pr Me i-Pr CF₃ Cl i-Pr Me CH₂CF₃CF₃ H Me H H CF₃ H Me H Me CF₃ H Me H Et CF₃ H Me H i-Pr CF₃ H Me HCH₂CF₃ CF₃ H Me Me H CF₃ H Me Me Me CF₃ H Me Me Et CF₃ H Me Me i-Pr CF₃H Me Me CH₂CF₃ CF₃ H Et H H CF₃ H Et H Me CF₃ H Et H Et CF₃ H Et H i-PrCF₃ H Et H CH₂CF₃ CF₃ H Et Me H CF₃ H Et Me Me CF₃ H Et Me Et CF₃ H EtMe i-Pr CF₃ H Et Me CH₂CF₃ CF₃ H i-Pr H H CF₃ H i-Pr H Me CF₃ H i-Pr HEt CF₃ H i-Pr H i-Pr CF₃ H i-Pr H CH₂CF₃ CF₃ H i-Pr Me H CF₃ H i-Pr MeMe CF₃ H i-Pr Me Et CF₃ H i-Pr Me i-Pr CF₃ H i-Pr Me CH₂CF₃ CF₃ H i-Bu HH CF₃ H i-Bu H Me CF₃ H i-Bu H Et CF₃ H i-Bu H i-Pr CF₃ H i-Bu H CH₂CF₃CF₃ H i-Bu Me H CF₃ H i-Bu Me Me CF₃ H i-Bu Me Et CF₃ H i-Bu Me i-Pr CF₃H i-Bu Me CH₂CF₃ CF₃ H CH₂OH H H CF₃ H CH₂OH H Me CF₃ H CH₂OH H Et CF₃ HCH₂OH H i-Pr CF₃ H CH₂OH H CH₂CF₃ CF₃ H CH₂OH Me H CF₃ H CH₂OH Me Me CF₃H CH₂OH Me Et CF₃ H CH₂OH Me i-Pr CF₃ H CH₂OH Me CH₂CF₃ CF₃ H CH₂OMe H HCF₃ H CH₂OMe H Me CF₃ H CH₂OMe H Et CF₃ H CH₂OMe H i-Pr CF₃ H CH₂OMe HCH₂CF₃ CF₃ H CH₂OMe Me H CF₃ H CH₂OMe Me Me CF₃ H CH₂OMe Me Et CF₃ HCH₂OMe Me i-Pr CF₃ H CH₂OMe Me CH₂CF₃ CF₃ Cl i-Bu H H CF₃ Cl i-Bu H MeCF₃ Cl i-Bu H Et CF₃ Cl i-Bu H i-Pr CF₃ Cl i-Bu H CH₂CF₃ CF₃ Cl i-Bu MeH CF₃ Cl i-Bu Me Me CF₃ Cl i-Bu Me Et CF₃ Cl i-Bu Me i-Pr CF₃ Cl i-Bu MeCH₂CF₃ CF₃ Cl CH₂OH H H CF₃ Cl CH₂OH H Me CF₃ Cl CH₂OH H Et CF₃ Cl CH₂OHH i-Pr CF₃ Cl CH₂OH H CH₂CF₃ CF₃ Cl CH₂OH Me H CF₃ Cl CH₂OH Me Me CF₃ ClCH₂OH Me Et CF₃ Cl CH₂OH Me i-Pr CF₃ Cl CH₂OH Me CH₂CF₃ CF₃ Cl CH₂OMe HH CF₃ Cl CH₂OMe H Me CF₃ Cl CH₂OMe H Et CF₃ Cl CH₂OMe H i-Pr CF₃ ClCH₂OMe H CH₂CF₃ CF₃ Cl CH₂OMe Me H CF₃ Cl CH₂OMe Me Me CF₃ Cl CH₂OMe MeEt CF₃ Cl CH₂OMe Me i-Pr CF₃ Cl CH₂OMe Me CH₂CF₃

TABLE 2-1

Q Q Q Q R^(1a) is Cl, R^(1b) is Cl, R⁵ is H 2-pyridinyl 3-pyridinyl4-pyridinyl 2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl3-pyrazinyl 3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl)5-(1,2,4-triazinyl) 6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl3-furanyl 2-thienyl 3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl1-Me-3-pyrrolyl 3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl1-Me-4-pyrazolyl 1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl1-Me-2-imidazolyl 1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl R^(1a)is CF₃, R^(1b) is H, R⁵ is H 2-pyridinyl 3-pyridinyl 4-pyridinyl2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl 3-pyrazinyl3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl) 5-(1,2,4-triazinyl)6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl 3-furanyl 2-thienyl3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl 1-Me-3-pyrrolyl3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl 1-Me-4-pyrazolyl1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl 1-Me-2-imidazolyl1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl R^(1a)is CF₃, R^(1b) is Cl, R⁵ is H 2-pyridinyl 3-pyridinyl 4-pyridinyl2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl 3-pyrazinyl3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl) 5-(1,2,4-triazinyl)6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl 3-furanyl 2-thienyl3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl 1-Me-3-pyrrolyl3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl 1-Me-4-pyrazolyl1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl 1-Me-2-imidazolyl1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl R^(1a)is Cl, R^(1b) is Cl, R⁵ is Me 2-pyridinyl 3-pyridinyl 4-pyridinyl2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl 3-pyrazinyl3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl) 5-(1,2,4-triazinyl)6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl 3-furanyl 2-thienyl3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl 1-Me-3-pyrrolyl3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl 1-Me-4-pyrazolyl1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl 1-Me-2-imidazolyl1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl R^(1a)is CF₃, R^(1b) is H, R⁵ is Me 2-pyridinyl 3-pyridinyl 4-pyridinyl2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl 3-pyrazinyl3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl) 5-(1,2,4-triazinyl)6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl 3-furanyl 2-thienyl3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl 1-Me-3-pyrrolyl3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl 1-Me-4-pyrazolyl1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl 1-Me-2-imidazolyl1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl R^(1a)is CF₃, R^(1b) is Cl, R⁵ is Me 2-pyridinyl 3-pyridinyl 4-pyridinyl2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl 3-pyrazinyl3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl) 5-(1,2,4-triazinyl)6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl 3-furanyl 2-thienyl3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl 1-Me-3-pyrrolyl3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl 1-Me-4-pyrazolyl1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl 1-Me-2-imidazolyl1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl

TABLE 2-2

Q Q Q Q R^(1a) is Cl, R^(1b) is Cl, R⁵ is Me 2-pyridinyl 3-pyridinyl4-pyridinyl 2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl3-pyrazinyl 3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl)5-(1,2,4-triazinyl) 6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl3-furanyl 2-thienyl 3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl1-Me-3-pyrrolyl 3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl1-Me-4-pyrazolyl 1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl1-Me-2-imidazolyl 1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl R^(1a)is CF₃, R^(1b) is H, R⁵ is Me 2-pyridinyl 3-pyridinyl 4-pyridinyl2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl 3-pyrazinyl3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl) 5-(1,2,4-triazinyl)6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl 3-furanyl 2-thienyl3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl 1-Me-3-pyrrolyl3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl 1-Me-4-pyrazolyl1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl 1-Me-2-imidazolyl1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl R^(1a)is CF₃, R^(1b) is Cl, R⁵ is Me 2-pyridinyl 3-pyridinyl 4-pyridinyl2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl 3-pyrazinyl3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl) 5-(1,2,4-triazinyl)6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl 3-furanyl 2-thienyl3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl 1-Me-3-pyrrolyl3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl 1-Me-4-pyrazolyl1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl 1-Me-2-imidazolyl1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl

TABLE 2-3

Q Q Q Q R^(1a) is Cl, R^(1b) is Cl, R⁵ is H 2-pyridinyl 3-pyridinyl4-pyridinyl 2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl3-pyrazinyl 3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl)5-(1,2,4-triazinyl) 6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl3-furanyl 2-thienyl 3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl1-Me-3-pyrrolyl 3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl1-Me-4-pyrazolyl 1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl1-Me-2-imidazolyl 1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl R^(1a)is CF₃, R^(1b) is H, R⁵ is H 2-pyridinyl 3-pyridinyl 4-pyridinyl2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl 3-pyrazinyl3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl) 5-(1,2,4-triazinyl)6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl 3-furanyl 2-thienyl3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl 1-Me-3-pyrrolyl3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl 1-Me-4-pyrazolyl1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl 1-Me-2-imidazolyl1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl R^(1a)is CF₃, R^(1b) is Cl, R⁵ is H 2-pyridinyl 3-pyridinyl 4-pyridinyl2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl 3-pyrazinyl3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl) 5-(1,2,4-triazinyl)6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl 3-furanyl 2-thienyl3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl 1-Me-3-pyrrolyl3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl 1-Me-4-pyrazolyl1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl 1-Me-2-imidazolyl1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl R^(1a)is Cl, R^(1b) is Cl, R⁵ is Me 2-pyridinyl 3-pyridinyl 4-pyridinyl2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl 3-pyrazinyl3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl) 5-(1,2,4-triazinyl)6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl 3-furanyl 2-thienyl3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl 1-Me-3-pyrrolyl3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl 1-Me-4-pyrazolyl1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl 1-Me-2-imidazolyl1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl R^(1a)is CF₃, R^(1b) is H, R⁵ is Me 2-pyridinyl 3-pyridinyl 4-pyridinyl2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl 3-pyrazinyl3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl) 5-(1,2,4-triazinyl)6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl 3-furanyl 2-thienyl3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl 1-Me-3-pyrrolyl3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl 1-Me-4-pyrazolyl1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl 1-Me-2-imidazolyl1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl R^(1a)is CF₃, R^(1b) is Cl, R⁵ is Me 2-pyridinyl 3-pyridinyl 4-pyridinyl2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl 3-pyrazinyl3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl) 5-(1,2,4-triazinyl)6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl 3-furanyl 2-thienyl3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl 1-Me-3-pyrrolyl3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl 1-Me-4-pyrazolyl1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl 1-Me-2-imidazolyl1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl

TABLE 2-4

Q Q Q Q R^(1a) is Cl, R^(1b) is Cl, R⁵ is Me 2-pyridinyl 3-pyridinyl4-pyridinyl 2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl3-pyrazinyl 3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl)5-(1,2,4-triazinyl) 6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl3-furanyl 2-thienyl 3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl1-Me-3-pyrrolyl 3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl1-Me-4-pyrazolyl 1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl1-Me-2-imidazolyl 1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl R^(1a)is CF₃, R^(1b) is H, R⁵ is Me 2-pyridinyl 3-pyridinyl 4-pyridinyl2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl 3-pyrazinyl3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl) 5-(1,2,4-triazinyl)6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl 3-furanyl 2-thienyl3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl 1-Me-3-pyrrolyl3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl 1-Me-4-pyrazolyl1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl 1-Me-2-imidazolyl1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl R^(1a)is CF₃, R^(1b) is Cl, R⁵ is Me 2-pyridinyl 3-pyridinyl 4-pyridinyl2-pyrimidinyl 4-pyrimidinyl 5-pyrimidinyl 2-pyrazinyl 3-pyrazinyl3-pyridazinyl 4-pyridazinyl 3-(1,2,4-triazinyl) 5-(1,2,4-triazinyl)6-(1,2,4-triazinyl) 2-(1,3,5-triazinyl) 2-furanyl 3-furanyl 2-thienyl3-thienyl 2-pyrrolyl 3-pyrrolyl 1-Me-2-pyrrolyl 1-Me-3-pyrrolyl3-pyrazolyl 4-pyrazolyl 5-pyrazolyl 1-Me-3-pyrazolyl 1-Me-4-pyrazolyl1-Me-5-pyrazolyl 2-imidazolyl 4-imidazolyl 1-Me-2-imidazolyl1-Me-4-imidazolyl 1-Me-5-imidazolyl 1,2,3-triazolyl1-Me-4-(1,2,3-triazolyl) 1-Me-5-(1,2,3-triazolyl) 1,2,4-triazolyl1-Me-3-(1,2,4-triazolyl) 1-Me-5-(1,2,4-triazolyl)2-Me-3-(1,2,4-triazolyl) 2-Me-5-(1,2,4-triazolyl)4-Me-3-(1,2,4-triazolyl) tetrazolyl 1-Me-5-(tetrazolyl)2-Me-5-(tetrazolyl) 2-oxazolyl 4-oxazolyl 5-oxazolyl 2-thiazolyl4-thiazolyl 5-thiazolyl 3-isoxazolyl 4-isoxazolyl 5-isoxazolyl3-isothiazolyl 4-isothiazolyl 5-isothiazolyl 4-(1,2,3-oxadiazolyl)5-(1,2,3-oxadiazolyl) 3-(1,2,4-oxadiazolyl) 5-(1,2,4-oxadiazolyl)1,3,4-oxadiazolyl 4-(1,2,3-thiadiazolyl) 5-(1,2,3-thiadiazolyl)3-(1,2,4-thiadiazolyl) 5-(1,2,4-thiadiazolyl) 1,3,4-thiadiazolyl

TABLE 3-1

R^(1a) R^(1b) R⁶ R⁷ R^(1a) R^(1b) R⁶ R⁷ Cl Cl H Me CF₃ H H Me Cl Cl H EtCF₃ H H Et Cl Cl Me Me CF₃ H Me Me Cl Cl Me Et CF₃ H Me Et CF₃ Cl H MeCF₃ Cl Me Me CF₃ Cl H Et CF₃ Cl Me Et

TABLE 3-2

R^(1a) R^(1b) R⁶ R⁷ R^(1a) R^(1b) R⁶ R⁷ Cl Cl H Me CF₃ H H Me Cl Cl H EtCF₃ H H Et Cl Cl Me Me CF₃ H Me Me Cl Cl Me Et CF₃ H Me Et CF₃ Cl H MeCF₃ Cl Me Me CF₃ Cl H Et CF₃ Cl Me Et

TABLE 4-1

R^(1a) R^(1b) R⁸ R^(1a) R^(1b) R⁸ X is —O— Cl Cl Me CF₃ H Me Cl Cl EtCF₃ H Et Cl Cl CH₂CF₃ CF₃ H CH₂CF₃ CF₃ Cl Me CF₃ Cl Et CF₃ Cl CH₂CF₃ Xis —C(O)— Cl Cl Me CF₃ H Me Cl Cl Et CF₃ H Et Cl Cl CH₂CF₃ CF₃ H CH₂CF₃CF₃ Cl Me CF₃ Cl Et CF₃ Cl CH₂CF₃

TABLE 4-2

R^(1a) R^(1b) R⁸ R^(1a) R^(1b) R⁸ X is —O— Cl Cl Me CF₃ H Me Cl Cl EtCF₃ H Et Cl Cl CH₂CF₃ CF₃ H CH₂CF₃ CF₃ Cl Me CF₃ Cl Et CF₃ Cl CH₂CF₃ Xis —C(O)— Cl Cl Me CF₃ H Me Cl Cl Et CF₃ H Et Cl Cl CH₂CF₃ CF₃ H CH₂CF₃CF₃ Cl Me CF₃ Cl Et CF₃ Cl CH₂CF₃

TABLE 5-1

R^(1a) R^(1b) R¹⁴ R¹⁵ R^(1a) R^(1b) R¹⁴ R¹⁵ Cl Cl Me H CF₃ H Me H Cl ClEt H CF₃ H Et H Cl Cl i-Pr H CF₃ H i-Pr H Cl Cl i-Bu H CF₃ H i-Bu H ClCl CH₂OH H CF₃ H CH₂OH H Cl Cl CH₂OMe H CF₃ H CH₂OMe H Cl Cl Me Me CF₃ HMe Me Cl Cl Et Me CF₃ H Et Me Cl Cl i-Pr Me CF₃ H i-Pr Me Cl Cl i-Bu MeCF₃ H i-Bu Me Cl Cl CH₂OH Me CF₃ H CH₂OH Me Cl Cl CH₂OMe Me CF₃ H CH₂OMeMe Cl Cl Me Et CF₃ H Me Et Cl Cl Et Et CF₃ H Et Et Cl Cl i-Pr Et CF₃ Hi-Pr Et Cl Cl i-Bu Et CF₃ H i-Bu Et Cl Cl CH₂OH Et CF₃ H CH₂OH Et Cl ClCH₂OMe Et CF₃ H CH₂OMe Et Cl Cl Me i-Pr CF₃ H Me i-Pr Cl Cl Et i-Pr CF₃H Et i-Pr Cl Cl i-Pr i-Pr CF₃ H i-Pr i-Pr Cl Cl i-Bu i-Pr CF₃ H i-Bui-Pr Cl Cl CH₂OH i-Pr CF₃ H CH₂OH i-Pr Cl Cl CH₂OMe i-Pr CF₃ H CH₂OMei-Pr Cl Cl Me CH₂CF₃ CF₃ H Me CH₂CF₃ Cl Cl Et CH₂CF₃ CF₃ H Et CH₂CF₃ ClCl i-Pr CH₂CF₃ CF₃ H i-Pr CH₂CF₃ Cl Cl i-Bu CH₂CF₃ CF₃ H i-Bu CH₂CF₃ ClCl CH₂OH CH₂CF₃ CF₃ H CH₂OH CH₂CF₃ Cl Cl CH₂OMe CH₂CF₃ CF₃ H CH₂OMeCH₂CF₃ CF₃ Cl Me H CF₃ Cl Me i-Pr CF₃ Cl Et H CF₃ Cl Et i-Pr CF₃ Cl i-PrH CF₃ Cl i-Pr i-Pr CF₃ Cl i-Bu H CF₃ Cl i-Bu i-Pr CF₃ Cl CH₂OH H CF₃ ClCH₂OH i-Pr CF₃ Cl CH₂OMe H CF₃ Cl CH₂OMe i-Pr CF₃ Cl Me Me CF₃ Cl MeCH₂CF₃ CF₃ Cl Et Me CF₃ Cl Et CH₂CF₃ CF₃ Cl i-Pr Me CF₃ Cl i-Pr CH₂CF₃CF₃ Cl i-Bu Me CF₃ Cl i-Bu CH₂CF₃ CF₃ Cl CH₂OH Me CF₃ Cl CH₂OH CH₂CF₃CF₃ Cl CH₂OMe Me CF₃ Cl CH₂OMe CH₂CF₃ CF₃ Cl Me Et CF₃ Cl Et Et CF₃ Cli-Pr Et CF₃ Cl i-Bu Et CF₃ Cl CH₂OH Et CF₃ Cl CH₂OMe Et

TABLE 5-2

R^(1a) R^(1b) R¹⁴ R¹⁵ R^(1a) R^(1b) R¹⁴ R¹⁵ Cl Cl Me H CF₃ H Me H Cl ClEt H CF₃ H Et H Cl Cl i-Pr H CF₃ H i-Pr H Cl Cl i-Bu H CF₃ H i-Bu H ClCl CH₂OH H CF₃ H CH₂OH H Cl Cl CH₂OMe H CF₃ H CH₂OMe H Cl Cl Me Me CF₃ HMe Me Cl Cl Et Me CF₃ H Et Me Cl Cl i-Pr Me CF₃ H i-Pr Me Cl Cl i-Bu MeCF₃ H i-Bu Me Cl Cl CH₂OH Me CF₃ H CH₂OH Me Cl Cl CH₂OMe Me CF₃ H CH₂OMeMe Cl Cl Me Et CF₃ H Me Et Cl Cl Et Et CF₃ H Et Et Cl Cl i-Pr Et CF₃ Hi-Pr Et Cl Cl i-Bu Et CF₃ H i-Bu Et Cl Cl CH₂OH Et CF₃ H CH₂OH Et Cl ClCH₂OMe Et CF₃ H CH₂OMe Et Cl Cl Me i-Pr CF₃ H Me i-Pr Cl Cl Et i-Pr CF₃H Et i-Pr Cl Cl i-Pr i-Pr CF₃ H i-Pr i-Pr Cl Cl i-Bu i-Pr CF₃ H i-Bui-Pr Cl Cl CH₂OH i-Pr CF₃ H CH₂OH i-Pr Cl Cl CH₂OMe i-Pr CF₃ H CH₂OMei-Pr Cl Cl Me CH₂CF₃ CF₃ H Me CH₂CF₃ Cl Cl Et CH₂CF₃ CF₃ H Et CH₂CF₃ ClCl i-Pr CH₂CF₃ CF₃ H i-Pr CH₂CF₃ Cl Cl i-Bu CH₂CF₃ CF₃ H i-Bu CH₂CF₃ ClCl CH₂OH CH₂CF₃ CF₃ H CH₂OH CH₂CF₃ Cl Cl CH₂OMe CH₂CF₃ CF₃ H CH₂OMeCH₂CF₃ CF₃ Cl Me H CF₃ Cl Me i-Pr CF₃ Cl Et H CF₃ Cl Et i-Pr CF₃ Cl i-PrH CF₃ Cl i-Pr i-Pr CF₃ Cl i-Bu H CF₃ Cl i-Bu i-Pr CF₃ Cl CH₂OH H CF₃ ClCH₂OH i-Pr CF₃ Cl CH₂OMe H CF₃ Cl CH₂OMe i-Pr CF₃ Cl Me Me CF₃ Cl MeCH₂CF₃ CF₃ Cl Et Me CF₃ Cl Et CH₂CF₃ CF₃ Cl i-Pr Me CF₃ Cl i-Pr CH₂CF₃CF₃ Cl i-Bu Me CF₃ Cl i-Bu CH₂CF₃ CF₃ Cl CH₂OH Me CF₃ Cl CH₂OH CH₂CF₃CF₃ Cl CH₂OMe Me CF₃ Cl CH₂OMe CH₂CF₃ CF₃ Cl Me Et CF₃ Cl Et Et CF₃ Cli-Pr Et CF₃ Cl i-Bu Et CF₃ Cl CH₂OH Et CF₃ Cl CH₂OMe Et

TABLE 5-3

R^(1a) R^(1b) R¹⁴ R¹⁵ R^(1a) R^(1b) R¹⁴ R¹⁵ Cl Cl Me H CF₃ H Me H Cl ClEt H CF₃ H Et H Cl Cl i-Pr H CF₃ H i-Pr H Cl Cl i-Bu H CF₃ H i-Bu H ClCl CH₂OH H CF₃ H CH₂OH H Cl Cl CH₂OMe H CF₃ H CH₂OMe H Cl Cl Me Me CF₃ HMe Me Cl Cl Et Me CF₃ H Et Me Cl Cl i-Pr Me CF₃ H i-Pr Me Cl Cl i-Bu MeCF₃ H i-Bu Me Cl Cl CH₂OH Me CF₃ H CH₂OH Me Cl Cl CH₂OMe Me CF₃ H CH₂OMeMe Cl Cl Me Et CF₃ H Me Et Cl Cl Et Et CF₃ H Et Et Cl Cl i-Pr Et CF₃ Hi-Pr Et Cl Cl i-Bu Et CF₃ H i-Bu Et Cl Cl CH₂OH Et CF₃ H CH₂OH Et Cl ClCH₂OMe Et CF₃ H CH₂OMe Et Cl Cl Me i-Pr CF₃ H Me i-Pr Cl Cl Et i-Pr CF₃H Et i-Pr Cl Cl i-Pr i-Pr CF₃ H i-Pr i-Pr Cl Cl i-Bu i-Pr CF₃ H i-Bui-Pr Cl Cl CH₂OH i-Pr CF₃ H CH₂OH i-Pr Cl Cl CH₂OMe i-Pr CF₃ H CH₂OMei-Pr Cl Cl Me CH₂CF₃ CF₃ H Me CH₂CF₃ Cl Cl Et CH₂CF₃ CF₃ H Et CH₂CF₃ ClCl i-Pr CH₂CF₃ CF₃ H i-Pr CH₂CF₃ Cl Cl i-Bu CH₂CF₃ CF₃ H i-Bu CH₂CF₃ ClCl CH₂OH CH₂CF₃ CF₃ H CH₂OH CH₂CF₃ Cl Cl CH₂OMe CH₂CF₃ CF₃ H CH₂OMeCH₂CF₃ CF₃ Cl Me H CF₃ Cl Me i-Pr CF₃ Cl Et H CF₃ Cl Et i-Pr CF₃ Cl i-PrH CF₃ Cl i-Pr i-Pr CF₃ Cl i-Bu H CF₃ Cl i-Bu i-Pr CF₃ Cl CH₂OH H CF₃ ClCH₂OH i-Pr CF₃ Cl CH₂OMe H CF₃ Cl CH₂OMe i-Pr CF₃ Cl Me Me CF₃ Cl MeCH₂CF₃ CF₃ Cl Et Me CF₃ Cl Et CH₂CF₃ CF₃ Cl i-Pr Me CF₃ Cl i-Pr CH₂CF₃CF₃ Cl i-Bu Me CF₃ Cl i-Bu CH₂CF₃ CF₃ Cl CH₂OH Me CF₃ Cl CH₂OH CH₂CF₃CF₃ Cl CH₂OMe Me CF₃ Cl CH₂OMe CH₂CF₃ CF₃ Cl Me Et CF₃ Cl Et Et CF₃ Cli-Pr Et CF₃ Cl i-Bu Et CF₃ Cl CH₂OH Et CF₃ Cl CH₂OMe Et

TABLE 5-4

R^(1a) R^(1b) R¹⁴ R¹⁵ R^(1a) R^(1b) R¹⁴ R¹⁵ Cl Cl Me H CF₃ H Me H Cl ClEt H CF₃ H Et H Cl Cl i-Pr H CF₃ H i-Pr H Cl Cl i-Bu H CF₃ H i-Bu H ClCl CH₂OH H CF₃ H CH₂OH H Cl Cl CH₂OMe H CF₃ H CH₂OMe H Cl Cl Me Me CF₃ HMe Me Cl Cl Et Me CF₃ H Et Me Cl Cl i-Pr Me CF₃ H i-Pr Me Cl Cl i-Bu MeCF₃ H i-Bu Me Cl Cl CH₂OH Me CF₃ H CH₂OH Me Cl Cl CH₂OMe Me CF₃ H CH₂OMeMe Cl Cl Me Et CF₃ H Me Et Cl Cl Et Et CF₃ H Et Et Cl Cl i-Pr Et CF₃ Hi-Pr Et Cl Cl i-Bu Et CF₃ H i-Bu Et Cl Cl CH₂OH Et CF₃ H CH₂OH Et Cl ClCH₂OMe Et CF₃ H CH₂OMe Et Cl Cl Me i-Pr CF₃ H Me i-Pr Cl Cl Et i-Pr CF₃H Et i-Pr Cl Cl i-Pr i-Pr CF₃ H i-Pr i-Pr Cl Cl i-Bu i-Pr CF₃ H i-Bui-Pr Cl Cl CH₂OH i-Pr CF₃ H CH₂OH i-Pr Cl Cl CH₂OMe i-Pr CF₃ H CH₂OMei-Pr Cl Cl Me CH₂CF₃ CF₃ H Me CH₂CF₃ Cl Cl Et CH₂CF₃ CF₃ H Et CH₂CF₃ ClCl i-Pr CH₂CF₃ CF₃ H i-Pr CH₂CF₃ Cl Cl i-Bu CH₂CF₃ CF₃ H i-Bu CH₂CF₃ ClCl CH₂OH CH₂CF₃ CF₃ H CH₂OH CH₂CF₃ Cl Cl CH₂OMe CH₂CF₃ CF₃ H CH₂OMeCH₂CF₃ CF₃ Cl Me H CF₃ Cl Me i-Pr CF₃ Cl Et H CF₃ Cl Et i-Pr CF₃ Cl i-PrH CF₃ Cl i-Pr i-Pr CF₃ Cl i-Bu H CF₃ Cl i-Bu i-Pr CF₃ Cl CH₂OH H CF₃ ClCH₂OH i-Pr CF₃ Cl CH₂OMe H CF₃ Cl CH₂OMe i-Pr CF₃ Cl Me Me CF₃ Cl MeCH₂CF₃ CF₃ Cl Et Me CF₃ Cl Et CH₂CF₃ CF₃ Cl i-Pr Me CF₃ Cl i-Pr CH₂CF₃CF₃ Cl i-Bu Me CF₃ Cl i-Bu CH₂CF₃ CF₃ Cl CH₂OH Me CF₃ Cl CH₂OH CH₂CF₃CF₃ Cl CH₂OMe Me CF₃ Cl CH₂OMe CH₂CF₃ CF₃ Cl Me Et CF₃ Cl Et Et CF₃ Cli-Pr Et CF₃ Cl i-Bu Et CF₃ Cl CH₂OH Et CF₃ Cl CH₂OMe Et

TABLE 6-1

R^(1a) R^(1b) R¹⁶ R^(1a) R^(1b) R¹⁶ Cl Cl Me CF₃ H Me Cl Cl F CF₃ H F ClCl NH₂ CF₃ H NH₂ CF₃ Cl Me CF₃ Cl F CF₃ Cl NH₂

TABLE 6-2

R^(1a) R^(1b) R¹⁶ R^(1a) R^(1b) R¹⁶ Cl Cl Me CF₃ H Me Cl Cl F CF₃ H F ClCl NH₂ CF₃ H NH₂ CF₃ Cl Me CF₃ Cl F CF₃ Cl NH₂

TABLE 7-1

R^(1a) R^(1b) J R^(1a) R^(1b) J Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl cyclopropyl CF₃ H cyclopropyl Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl

CF₃ H

CF₃ Cl

CF₃ Cl

CF₃ Cl

CF₃ Cl

CF₃ Cl

CF₃ Cl cyclopropyl CF₃ Cl

CF₃ Cl

CF₃ Cl

CF₃ Cl

CF₃ Cl

CF₃ Cl

TABLE 7-2

R^(1a) R^(1b) J R^(1a) R^(1b) J Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl cyclopropyl CF₃ H cyclopropyl Cl Cl

CF₃ H

Cl Cl

CF₃ H

Cl Cl

CF₃ H

CF₃ Cl

CF₃ Cl

CF₃ Cl

CF₃ Cl

CF₃ Cl

CF₃ Cl cyclopropyl CF₃ Cl

CF₃ Cl

CF₃ Cl

CF₃ Cl

CF₃ Cl

CF₃ Cl

Specific compounds of Formula 1, prepared by the methods and variationsas described in preceding Schemes 1-11 and Synthesis Examples 1-5, areshown in the Index Tables below. The following abbreviations may beused: Cmpd means Compound, t is tertiary, c is cyclo, Me is methyl, Etis ethyl and Ph is phenyl. The abbreviation “Ex.” stands for “Example”and is followed by a number indicating in which Synthesis Example thecompound is prepared.

Melting point data (MP) is reported as a temperature range (for example,122-126). Mass spectral data (MS) is reported as a single numericalvalue (for example, 542). For mass spectral data (AP⁺ (M+1)), thenumerical value reported is the molecular weight of the parent molecularion (M) formed by addition of H⁺ (molecular weight of 1) to the moleculeto give a M+1 peak observed by mass spectrometry using atmosphericpressure chemical ionization (AP⁺). The alternate molecular ion peaks(e.g., M+2 or M+4) that occur with compounds containing multiplehalogens are not reported.

INDEX TABLE A

Cmpd. MP/ No. R^(1a) R^(1b) J MS data 1 Cl Cl

542 2 CF₃ Cl

575 3 Cl Cl

556 4 Cl Cl

570 5 Cl Cl

 78-82 6 Cl Cl

122-126 7 Cl Cl

147-151 43 CF₃ H

106-110 44 Cl Cl

584 45 Cl Cl

572 46 Cl Cl

570 47 Cl Cl

595 48 Cl Cl

581

INDEX TABLE A-1

Cmpd. No. R^(1a) J MS data 8 Cl

542

INDEX TABLE A-2

Cmpd. No. R^(1a) J MS data 9 Cl

542

INDEX TABLE B

Cmpd. MP/ No. R^(1a) R^(1b) J MS data 10 Cl Cl

563 11 CF₃ Cl

597 12 Cl Cl

563 13 Cl Cl

563 14 Cl Cl

563 15 Cl Cl

562 16 Cl Cl

563 17 Cl Cl

563 18 Cl Cl

576 19 Cl Cl

577 20 Cl Cl

576 21 Cl Cl

577 22 Cl Cl

565 23 Cl Cl

551 24 Cl Cl

552 25 Cl Cl

566 26 Cl Cl

553 27 Cl Cl

566 28 Cl Cl

568 29 Cl Cl

551 30 Cl Cl

551 31 Cl Cl

565 32 Cl Cl

631 49 CF₃ H

151-155 50 CF₃ H

153-157 51 CF₃ H

563 52 Cl Cl

631 53 Cl Cl

593 54 Cl Cl

207-208 55 Cl Cl

 69-71 56 Cl Cl

183-184 57 Cl Cl

202-203 58 Cl Cl

577 59 Cl Cl

577 60 Cl Cl

590

INDEX TABLE B-1

Cmpd. MP/ No. R^(1a) R^(1b) J MS data 61 Cl Cl

120-124 63 Cl Cl

577

INDEX TABLE B-2

Cmpd. No. R^(1a) R^(1b) J MS data 62 Cl Cl

563

INDEX TABLE C

Cmpd. No. R^(1a) J MS data 33 Cl

528

INDEX TABLE D

Cmpd. No. R^(1a) J MS data 34 Cl

584 64 Cl

582

INDEX TABLE E

Cmpd. MP/ No. R^(1a) R^(1b) J MS data 35 Cl Cl

543 36 CF₃ Cl

577 37 CF₃ Cl

563 38 Cl Cl

529 39 Cl Cl

557 40 Cl Cl

543 41 Cl Cl

587 42 Cl Cl

573 65 CF₃ H

161-165 66 CF₃ H

 79-83

INDEX TABLE F

Cmpd. MP/ No. R^(1a) R^(1b) J MS data 67 CF₃ H cyclopropyl 153-157 68CF₃ H

200-204 69 CF₃ H

524 70 Cl Cl cyclopropyl 511 71 Cl Cl

524 72 Cl Cl

256-260 73 Cl Cl

525.1 74 Cl Cl

538.2 75 Cl Cl

 94-98 76 Cl Cl

135-139 77 Cl Cl

536 78 Cl Cl

550

INDEX TABLE G

Cmpd. No. R^(1a) R^(1b) J MS data 79 Cl Cl

604

A compound of this invention will generally be used as an invertebratepest control active ingredient in a composition, i.e. formulation, withat least one additional component selected from the group consisting ofsurfactants, solid diluents and liquid diluents, which serves as acarrier. The formulation or composition ingredients are selected to beconsistent with the physical properties of the active ingredient, modeof application and environmental factors such as soil type, moisture andtemperature.

Useful formulations include both liquid and solid compositions. Liquidcompositions include solutions (including emulsifiable concentrates),suspensions, emulsions (including microemulsions, oil in wateremulsions, flowable concentrates and/or suspoemulsions) and the like,which optionally can be thickened into gels. The general types ofaqueous liquid compositions are soluble concentrate, suspensionconcentrate, capsule suspension, concentrated emulsion, microemulsion,oil in water emulsion, flowable concentrate and suspoemulsion. Thegeneral types of nonaqueous liquid compositions are emulsifiableconcentrate, microemulsifiable concentrate, dispersible concentrate andoil dispersion.

The general types of solid compositions are dusts, powders, granules,pellets, prills, pastilles, tablets, filled films (including seedcoatings) and the like, which can be water-dispersible (“wettable”) orwater-soluble. Films and coatings formed from film-forming solutions orflowable suspensions are particularly useful for seed treatment. Activeingredient can be (micro)encapsulated and further formed into asuspension or solid formulation; alternatively the entire formulation ofactive ingredient can be encapsulated (or “overcoated”). Encapsulationcan control or delay release of the active ingredient. An emulsifiablegranule combines the advantages of both an emulsifiable concentrateformulation and a dry granular formulation. High-strength compositionsare primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable mediumbefore spraying. Such liquid and solid formulations are formulated to bereadily diluted in the spray medium, usually water, but occasionallyanother suitable medium like an aromatic or paraffinic hydrocarbon orvegetable oil. Spray volumes can range from about one to severalthousand liters per hectare, but more typically are in the range fromabout ten to several hundred liters per hectare. Sprayable formulationscan be tank mixed with water or another suitable medium for foliartreatment by aerial or ground application, or for application to thegrowing medium of the plant. Liquid and dry formulations can be metereddirectly into drip irrigation systems or metered into the furrow duringplanting. Liquid and solid formulations can be applied onto seeds ofcrops and other desirable vegetation as seed treatments before plantingto protect developing roots and other subterranean plant parts and/orfoliage through systemic uptake.

The formulations will typically contain effective amounts of activeingredient, diluent and surfactant within the following approximateranges which add up to 100 percent by weight.

Weight Percent Active Ingredient Diluent Surfactant Water-Dispersibleand Water- 0.001-90 0-99.999 0-15 soluble Granules, Tablets and PowdersOil Dispersions, Suspensions,    1-50 40-99    0-50 Emulsions, Solutions(including Emulsifiable Concentrates) Dusts    1-25 70-99    0-5 Granules and Pellets 0.001-99 5-99.999 0-15 High Strength Compositions  90-99 0-10    0-2 

Solid diluents include, for example, clays such as bentonite,montmorillonite, attapulgite and kaolin, gypsum, cellulose, titaniumdioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose),silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodiumcarbonate and bicarbonate, and sodium sulfate. Typical solid diluentsare described in Watkins et al., Handbook of Insecticide Dust Diluentsand Carriers, 2nd Ed., Dorland Books, Caldwell, N.J.

Liquid diluents include, for example, water, N,N-dimethylalkanamides(e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide,N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates(e.g., triethylphosphate), ethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol, polypropylene glycol, propylenecarbonate, butylene carbonate, paraffins (e.g., white mineral oils,normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes,glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons,dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones suchas cyclohexanone, 2-heptanone, isophorone and4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexylacetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetateand isobornyl acetate, other esters such as alkylated lactate esters,dibasic esters alkyl and aryl benzoates, γ-butyrolactone, and alcohols,which can be linear, branched, saturated or unsaturated, such asmethanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutylalcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecylalcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecylalcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol,diacetone alcohol, cresol and benzyl alcohol. Liquid diluents alsoinclude glycerol esters of saturated and unsaturated fatty acids(typically C₆-C₂₂), such as plant seed and fruit oils (e.g., oils ofolive, castor, linseed, sesame, corn (maize), peanut, sunflower,grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palmkernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, codliver oil, fish oil), and mixtures thereof. Liquid diluents also includealkylated fatty acids (e.g., methylated, ethylated, butylated) whereinthe fatty acids may be obtained by hydrolysis of glycerol esters fromplant and animal sources, and can be purified by distillation. Typicalliquid diluents are described in Marsden, Solvents Guide, 2nd Ed.,Interscience, New York, 1950.

The solid and liquid compositions of the present invention often includeone or more surfactants. When added to a liquid, surfactants (also knownas “surface-active agents”) generally modify, most often reduce, thesurface tension of the liquid. Depending on the nature of thehydrophilic and lipophilic groups in a surfactant molecule, surfactantscan be useful as wetting agents, dispersants, emulsifiers or defoamingagents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionicsurfactants useful for the present compositions include, but are notlimited to: alcohol alkoxylates such as alcohol alkoxylates based onnatural and synthetic alcohols (which may be branched or linear) andprepared from the alcohols and ethylene oxide, propylene oxide, butyleneoxide or mixtures thereof; amine ethoxylates, alkanolamides andethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylatedsoybean, castor and rapeseed oils; alkylphenol alkoxylates such asoctylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenolethoxylates and dodecyl phenol ethoxylates (prepared from the phenolsand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); block polymers prepared from ethylene oxide or propylene oxideand reverse block polymers where the terminal blocks are prepared frompropylene oxide; ethoxylated fatty acids; ethoxylated fatty esters andoils; ethoxylated methyl esters; ethoxylated tristyrylphenol (includingthose prepared from ethylene oxide, propylene oxide, butylene oxide ormixtures thereof); fatty acid esters, glycerol esters, lanolin-basedderivatives, polyethoxylate esters such as polyethoxylated sorbitanfatty acid esters, polyethoxylated sorbitol fatty acid esters andpolyethoxylated glycerol fatty acid esters; other sorbitan derivativessuch as sorbitan esters; polymeric surfactants such as randomcopolymers, block copolymers, alkyd peg (polyethylene glycol) resins,graft or comb polymers and star polymers; polyethylene glycols (pegs);polyethylene glycol fatty acid esters; silicone-based surfactants; andsugar-derivatives such as sucrose esters, alkyl polyglycosides and alkylpolysaccharides.

Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; carboxylated alcohol or alkylphenolethoxylates; diphenyl sulfonate derivatives; lignin and ligninderivatives such as lignosulfonates; maleic or succinic acids or theiranhydrides; olefin sulfonates; phosphate esters such as phosphate estersof alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates andphosphate esters of styryl phenol ethoxylates; protein-basedsurfactants; sarcosine derivatives; styryl phenol ether sulfate;sulfates and sulfonates of oils and fatty acids; sulfates and sulfonatesof ethoxylated alkylphenols; sulfates of alcohols; sulfates ofethoxylated alcohols; sulfonates of amines and amides such asN,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, anddodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes;sulfonates of naphthalene and alkyl naphthalene; sulfonates offractionated petroleum; sulfosuccinamates; and sulfosuccinates and theirderivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides andethoxylated amides; amines such as N-alkyl propanediamines,tripropylenetriamines and dipropylenetetramines, and ethoxylated amines,ethoxylated diamines and propoxylated amines (prepared from the aminesand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); amine salts such as amine acetates and diamine salts;quaternary ammonium salts such as quaternary salts, ethoxylatedquaternary salts and diquaternary salts; and amine oxides such asalkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic andanionic surfactants or mixtures of nonionic and cationic surfactants.Nonionic, anionic and cationic surfactants and their recommended usesare disclosed in a variety of published references includingMcCutcheon's Emulsifiers and Detergents, annual American andInternational Editions published by McCutcheon's Division, TheManufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopediaof Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; andA. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition,John Wiley and Sons, New York, 1987.

Compositions of this invention may also contain formulation auxiliariesand additives, known to those skilled in the art as formulation aids(some of which may be considered to also function as solid diluents,liquid diluents or surfactants). Such formulation auxiliaries andadditives may control: pH (buffers), foaming during processing(antifoams such polyorganosiloxanes), sedimentation of activeingredients (suspending agents), viscosity (thixotropic thickeners),in-container microbial growth (antimicrobials), product freezing(antifreezes), color (dyes/pigment dispersions), wash-off (film formersor stickers), evaporation (evaporation retardants), and otherformulation attributes. Film formers include, for example, polyvinylacetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinylacetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers andwaxes. Examples of formulation auxiliaries and additives include thoselisted in McCutcheon's Volume 2: Functional Materials, annualInternational and North American editions published by McCutcheon'sDivision, The Manufacturing Confectioner Publishing Co.; and PCTPublication WO 03/024222.

The compound of Formula 1 and any other active ingredients are typicallyincorporated into the present compositions by dissolving the activeingredient in a solvent or by grinding in a liquid or dry diluent.Solutions, including emulsifiable concentrates, can be prepared bysimply mixing the ingredients. If the solvent of a liquid compositionintended for use as an emulsifiable concentrate is water-immiscible, anemulsifier is typically added to emulsify the active-containing solventupon dilution with water. Active ingredient slurries, with particlediameters of up to 2,000 μm can be wet milled using media mills toobtain particles with average diameters below 3 μm. Aqueous slurries canbe made into finished suspension concentrates (see, for example, U.S.Pat. No. 3,060,084) or further processed by spray drying to formwater-dispersible granules. Dry formulations usually require dry millingprocesses, which produce average particle diameters in the 2 to 10 μmrange. Dusts and powders can be prepared by blending and usuallygrinding (such as with a hammer mill or fluid-energy mill). Granules andpellets can be prepared by spraying the active material upon preformedgranular carriers or by agglomeration techniques. See Browning,“Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry'sChemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963,pages 8-57 and following, and WO 91/13546. Pellets can be prepared asdescribed in U.S. Pat. No. 4,172,714. Water-dispersible andwater-soluble granules can be prepared as taught in U.S. Pat. Nos.4,144,050, 3,920,442 and DE 3,246,493. Tablets can be prepared as taughtin U.S. Pat. Nos. 5,180,587, 5,232,701 and 5,208,030. Films can beprepared as taught in GB 2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see T. S.Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture”in Pesticide Chemistry and Bioscience, The Food-Environment Challenge,T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th InternationalCongress on Pesticide Chemistry, The Royal Society of Chemistry,Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6,line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No.3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12,15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 andExamples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons,Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8thEd., Blackwell Scientific Publications, Oxford, 1989; and Developmentsin formulation technology, PJB Publications, Richmond, U K, 2000.

In the following Examples, all formulations are prepared in conventionalways. Compound numbers refer to compounds in Index Tables A-G. Withoutfurther elaboration, it is believed that one skilled in the art usingthe preceding description can utilize the present invention to itsfullest extent. The following Examples are, therefore, to be construedas merely illustrative, and not limiting of the disclosure in any waywhatsoever. Percentages are by weight except where otherwise indicated.

Example A

High Strength Concentrate Compound 1 98.5% silica aerogel  0.5%synthetic amorphous fine silica  1.0%

Example B

Wettable Powder Compound 3 65.0% dodecylphenol polyethylene glycol ether2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0%montmorillonite (calcined) 23.0%

Example C

Granule Compound 8 10.0% attapulgite granules (low volatile matter,90.0% 0.71/0.30 mm; U.S.S. No. 25-50 sieves)

Example D

Extruded Pellet Compound 10 25.0% anhydrous sodium sulfate 10.0% crudecalcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0%calcium/magnesium bentonite 59.0%

Example E

Emulsifiable Concentrate Compound 11 10.0% polyoxyethylene sorbitolhexoleate 20.0% C₆-C₁₀ fatty acid methyl ester 70.0%

Example F

Microemulsion Compound 19 5.0% polyvinylpyrrolidone-vinyl acetatecopolymer 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water20.0%

Example G

Seed Treatment Compound 20 20.00% polyvinylpyrrolidone-vinyl acetatecopolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00%polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol(POE 20) 2.00% polyorganosilane 0.20% colorant red dye 0.05% water65.75%

Example H

Fertilizer Stick Compound 33 2.5% pyrrolidone-styrene copolymer 4.8%tristyrylphenyl 16-ethoxylate 2.3% talc 0.8% corn starch 5.0%slow-release fertilizer 36.0% kaolin 38.0% water 10.6%

Example I

Suspension Concentrate compound 34  35% butylpolyoxyethylene/polypropylene block copolymer 4.0% stearicacid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0%xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%1,2-benzisothiazolin-3-one 0.1% water 53.7% 

Example J

Emulsion in Water compound 39 10.0%  butyl polyoxyethylene/polypropyleneblock copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0%styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0%silicone based defoamer 0.1% 1,2-benzisothiazolin-3-one 0.1% aromaticpetroleum based hydrocarbon 20.0 water 58.7% 

Example K

Oil Dispersion compound 50   25% polyoxyethylene sorbitol hexaoleate  15% organically modified bentonite clay  2.5% fatty acid methyl ester57.5%

Example L

Suspoemulsion compound 61 10.0% imidacloprid 5.0% butylpolyoxyethylene/polypropylene block copolymer 4.0% stearicacid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0%xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%1,2-benzisothiazolin-3-one 0.1% aromatic petroleum based hydrocarbon20.0% water 53.7%

Example M

Suspension Concentrate compound 67  35% butylpolyoxyethylene/polypropylene block copolymer 4.0% stearicacid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0%xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%1,2-benzisothiazolin-3-one 0.1% water 53.7% 

Example N

Emulsion in Water compound 69 10.0% butyl polyoxyethylene/polypropyleneblock copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0%styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0%silicone based defoamer 0.1% 1,2-benzisothiazolin-3-one 0.1% aromaticpetroleum based hydrocarbon 20.0 water 58.7%

Example O

Oil Dispersion compound 70   25% polyoxyethylene sorbitol hexaoleate  15% organically modified bentonite clay  2.5% fatty acid methyl ester57.5%

Example P

Suspoemulsion compound 71 10.0% imidacloprid 5.0% butylpolyoxyethylene/polypropylene block 4.0% copolymer stearicacid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0%xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%1,2-benzisothiazolin-3-one 0.1% aromatic petroleum based hydrocarbon20.0% water 53.7%

Compounds of this invention exhibit activity against a wide spectrum ofinvertebrate pests. These pests include invertebrates inhabiting avariety of environments such as, for example, plant foliage, roots,soil, harvested crops or other foodstuffs, or building structures. Thesepests include, for example, invertebrates feeding on foliage (includingleaves, stems, flowers and fruits), seeds, wood or textile fibers, andthereby causing injury or damage to, for example, growing or storedagronomic crops, forests, greenhouse crops, ornamentals, nursery crops,stored foodstuffs or fiber products, or houses or other structures ortheir contents. Those skilled in the art will appreciate that not allcompounds are equally effective against all growth stages of all pests.

These present compounds and compositions are thus useful agronomicallyfor protecting field crops from phytophagous invertebrate pests, andalso nonagronomically for protecting other horticultural crops andplants from phytophagous invertebrate pests. This utility includesprotecting crops and other plants (i.e. both agronomic and nonagronomic)that contain genetic material introduced by genetic engineering (i.e.transgenic) or modified by mutagenesis to provide advantageous traits.Examples of such traits include tolerance to herbicides, resistance tophytophagous pests (e.g., insects, mites, aphids, spiders, nematodes,snails, plant-pathogenic fungi, bacteria and viruses), improved plantgrowth, increased tolerance of adverse growing conditions such as highor low temperatures, low or high soil moisture, and high salinity,increased flowering or fruiting, greater harvest yields, more rapidmaturation, higher quality and/or nutritional value of the harvestedproduct, or improved storage or process properties of the harvestedproducts. Transgenic plants can be modified to express multiple traits.Examples of plants containing traits provided by genetic engineering ormutagenesis include varieties of corn, cotton, soybean and potatoexpressing an insecticidal Bacillus thuringiensis toxin such as YIELDGARD®, KNOCKOUT®, STARLINK®, BOLLGARD®, NuCOTN® and NEWLEAF®, INVICTARR2 PRO™, and herbicide-tolerant varieties of corn, cotton, soybean andrapeseed such as ROUNDUP READY®, LIBERTY LINK®, IMI®, STS® andCLEARFIELD®, as well as crops expressing N-acetyltransferase (GAT) toprovide resistance to glyphosate herbicide, or crops containing the HRAgene providing resistance to herbicides inhibiting acetolactate synthase(ALS). The present compounds and compositions may exhibit enhancedeffects with traits introduced by genetic engineering or modified bymutagenesis, thus enhancing phenotypic expression or effectiveness ofthe traits or increasing the invertebrate pest control effectiveness ofthe present compounds and compositions. In particular, the presentcompounds and compositions may exhibit enhance effects with thephenotypic expression of proteins or other natural products toxic toinvertebrate pests to provide greater-than-additive control of thesepests.

Compositions of this invention can also optionally comprise plantnutrients, e.g., a fertilizer composition comprising at least one plantnutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium,magnesium, iron, copper, boron, manganese, zinc, and molybdenum. Of noteare compositions comprising at least one fertilizer compositioncomprising at least one plant nutrient selected from nitrogen,phosphorus, potassium, sulfur, calcium and magnesium. Compositions ofthe present invention which further comprise at least one plant nutrientcan be in the form of liquids or solids. Of note are solid formulationsin the form of granules, small sticks or tablets. Solid formulationscomprising a fertilizer composition can be prepared by mixing thecompound or composition of the present invention with the fertilizercomposition together with formulating ingredients and then preparing theformulation by methods such as granulation or extrusion. Alternativelysolid formulations can be prepared by spraying a solution or suspensionof a compound or composition of the present invention in a volatilesolvent onto a previous prepared fertilizer composition in the form ofdimensionally stable mixtures, e.g., granules, small sticks or tablets,and then evaporating the solvent.

Nonagronomic uses refer to invertebrate pest control in the areas otherthan fields of crop plants. Nonagronomic uses of the present compoundsand compositions include control of invertebrate pests in stored grains,beans and other foodstuffs, and in textiles such as clothing andcarpets. Nonagronomic uses of the present compounds and compositionsalso include invertebrate pest control in ornamental plants, forests, inyards, along roadsides and railroad rights of way, and on turf such aslawns, golf courses and pastures. Nonagronomic uses of the presentcompounds and compositions also include invertebrate pest control inhouses and other buildings which may be occupied by humans and/orcompanion, farm, ranch, zoo or other animals. Nonagronomic uses of thepresent compounds and compositions also include the control of pestssuch as termites that can damage wood or other structural materials usedin buildings.

Examples of agronomic or nonagronomic invertebrate pests include eggs,larvae and adults of the order Lepidoptera, such as armyworms, cutworms,loopers, and heliothines in the family Noctuidae (e.g., pink stem borer(Sesamia inferens Walker), corn stalk borer (Sesamia nonagrioidesLefebvre), southern armyworm (Spodoptera eridania Cramer), fall armyworm(Spodoptera frugiperda J. E. Smith), beet armyworm (Spodoptera exiguaHübner), cotton leafworm (Spodoptera littoralis Boisduval), yellowstriped armyworm (Spodoptera ornithogalli Guenée), black cutworm(Agrotis ipsilon Hufnagel), velvetbean caterpillar (Anticarsiagemmatalis Hübner), green fruitworm (Lithophane antennata Walker),cabbage armyworm (Barathra brassicae Linnaeus), soybean looper(Pseudoplusia includens Walker), cabbage looper (Trichoplusia niHübner), tobacco budworm (Heliothis virescens Fabricius)); borers,casebearers, webworms, coneworms, cabbageworms and skeletonizers fromthe family Pyralidae (e.g., European corn borer (Ostrinia nubilalisHübner), navel orangeworm (Amyelois transitella Walker), corn rootwebworm (Crambus caliginosellus Clemens), sod webworms (Pyralidae:Crambinae) such as sod worm (Herpetogramma licarsisalis Walker),sugarcane stem borer (Chilo infuscatellus Snellen), tomato small borer(Neoleucinodes elegantalis Guenée), green leafroller (Cnaphalocrocismedinalis), grape leaffolder (Desmia funeralis Hübner), melon worm(Diaphania nitidalis Stoll), cabbage center grub (Helluala hydralisGuenée), yellow stem borer (Scirpophaga incertulas Walker), early shootborer (Scirpophaga infuscatellus Snellen), white stem borer (Scirpophagainnotata Walker), top shoot borer (Scirpophaga nivella Fabricius),dark-headed rice borer (Chilo polychrysus Meyrick), striped riceborer(Chilo suppressalis Walker), cabbage cluster caterpillar (Crocidolomiabinotalis English)); leafrollers, budworms, seed worms, and fruit wormsin the family Tortricidae (e.g., codling moth (Cydia pomonellaLinnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruitmoth (Grapholita molesta Busck), citrus false codling moth(Cryptophlebia leucotreta Meyrick), citrus borer (Ecdytolopha aurantianaLima), redbanded leafroller (Argyrotaenia velutinana Walker),obliquebanded leafroller (Choristoneura rosaceana Harris), light brownapple moth (Epiphyas postvittana Walker), European grape berry moth(Eupoecilia ambiguella Hübner), apple bud moth (Pandemis pyrusanaKearfott), omnivorous leafroller (Platynota stultana Walsingham), barredfruit-tree tortrix (Pandemis cerasana Hübner), apple brown tortrix(Pandemis heparana Denis & Schiffermúller)); and many other economicallyimportant lepidoptera (e.g., diamondback moth (Plutella xylostellaLinnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth(Lymantria dispar Linnaeus), peach fruit borer (Carposina niponensisWalsingham), peach twig borer (Anarsia lineatella Zeller), potatotuberworm (Phthorimaea operculella Zeller), spotted teniform leafminer(Lithocolletis blancardella Fabricius), Asiatic apple leafminer(Lithocolletis ringoniella Matsumura), rice leaffolder (Lerodea eufalaEdwards), apple leafminer (Leucoptera scitella Zeller)); eggs, nymphsand adults of the order Blattodea including cockroaches from thefamilies Blattellidae and Blattidae (e.g., oriental cockroach (Blattaorientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo),German cockroach (Blattella germanica Linnaeus), brownbanded cockroach(Supella longipalpa Fabricius), American cockroach (Periplanetaamericana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister),Madeira cockroach (Leucophaea maderae Fabricius)), smoky brown cockroach(Periplaneta fuliginosa Service), Australian Cockroach (Periplanetaaustralasiae Fabr.), lobster cockroach (Nauphoeta cinerea Olivier) andsmooth cockroach (Symploce pallens Stephens)); eggs, foliar feeding,fruit feeding, root feeding, seed feeding and vesicular tissue feedinglarvae and adults of the order Coleoptera including weevils from thefamilies Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil(Anthonomus grandis Boheman), rice water weevil (Lissorhoptrusoryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus),rice weevil (Sitophilus oryzae Linnaeus)), annual bluegrass weevil(Listronotus maculicollis Dietz), bluegrass billbug (Sphenophorusparvulus Gyllenhal), hunting billbug (Sphenophorus venatus vestitus),Denver billbug (Sphenophorus cicatristriatus Fahraeus)); flea beetles,cucumber beetles, rootworms, leaf beetles, potato beetles, andleafminers in the family Chrysomelidae (e.g., Colorado potato beetle(Leptinotarsa decemlineata Say), western corn rootworm (Diabroticavirgifera virgifera LeConte)); chafers and other beetles from the familyScarabaeidae (e.g., Japanese beetle (Popillia japonica Newman), orientalbeetle (Anomala orientalis Waterhouse, Exomala orientalis (Waterhouse)Baraud), northern masked chafer (Cyclocephala borealis Arrow), southernmasked chafer (Cyclocephala immaculata Olivier or C. lurida Bland), dungbeetle and white grub (Aphodius spp.), black turfgrass ataenius(Ataenius spretulus Haldeman), green June beetle (Cotinis nitidaLinnaeus), Asiatic garden beetle (Maladera castanea Arrow), May/Junebeetles (Phyllophaga spp.) and European chafer (Rhizotrogus majalisRazoumowsky)); carpet beetles from the family Dermestidae; wirewormsfrom the family Elateridae; bark beetles from the family Scolytidae andflour beetles from the family Tenebrionidae.

In addition, agronomic and nonagronomic pests include: eggs, adults andlarvae of the order Dermaptera including earwigs from the familyForficulidae (e.g., European earwig (Forficula auricularia Linnaeus),black earwig (Chelisoches morio Fabricius)); eggs, immatures, adults andnymphs of the orders Hemiptera and Homoptera such as, plant bugs fromthe family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g.Empoasca spp.) from the family Cicadellidae, bed bugs (e.g., Cimexlectularius Linnaeus) from the family Cimicidae, planthoppers from thefamilies Fulgoroidae and Delphacidae, treehoppers from the familyMembracidae, psyllids from the family Psyllidae, whiteflies from thefamily Aleyrodidae, aphids from the family Aphididae, phylloxera fromthe family Phylloxeridae, mealybugs from the family Pseudococcidae,scales from the families Coccidae, Diaspididae and Margarodidae, lacebugs from the family Tingidae, stink bugs from the family Pentatomidae,chinch bugs (e.g., hairy chinch bug (Blissus leucopterus hirtusMontandon) and southern chinch bug (Blissus insularis Barber)) and otherseed bugs from the family Lygaeidae, spittlebugs from the familyCercopidae squash bugs from the family Coreidae, and red bugs and cottonstainers from the family Pyrrhocoridae.

Agronomic and nonagronomic pests also include: eggs, larvae, nymphs andadults of the order Acari (mites) such as spider mites and red mites inthe family Tetranychidae (e.g., European red mite (Panonychus ulmiKoch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite(Tetranychus mcdanieli McGregor)); flat mites in the familyTenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor));rust and bud mites in the family Eriophyidae and other foliar feedingmites, dust mites in the family Epidermoptidae, follicle mites in thefamily Demodicidae, grain mites in the family Glycyphagidae; ticks inthe family Ixodidae, commonly known as hard ticks (e.g., deer tick(Ixodes scapularis Say), Australian paralysis tick (Ixodes holocyclusNeumann), American dog tick (Dermacentor variabilis Say), lone star tick(Amblyomma americanum Linnaeus)) and ticks in the family Argasidae,commonly known as soft ticks (e.g., relapsing fever tick (Ornithodorosturicata), common fowl tick (Argas radiatus)); scab and itch mites inthe families Psoroptidae, Pyemotidae, and Sarcoptidae; eggs, adults andimmatures of the order Orthoptera including grasshoppers, locusts andcrickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipesFabricius, M. differentialis Thomas), American grasshoppers (e.g.,Schistocerca americana Drury), desert locust (Schistocerca gregariaForskal), migratory locust (Locusta migratoria Linnaeus), bush locust(Zonocerus spp.), house cricket (Acheta domesticus Linnaeus), molecrickets (e.g., tawny mole cricket (Scapteriscus vicinus Scudder) andsouthern mole cricket (Scapteriscus borellii Giglio-Tos)); eggs, adultsand immatures of the order Diptera including leafminers (e.g., Liriomyzaspp. such as serpentine vegetable leafminer (Liriomyza sativaeBlanchard)), midges, fruit flies (Tephritidae), frit flies (e.g.,Oscinella frit Linnaeus), soil maggots, house flies (e.g., Muscadomestica Linnaeus), lesser house flies (e.g., Fannia canicularisLinnaeus, F. femoralis Stein), stable flies (e.g., Stomoxys calcitransLinnaeus), face flies, horn flies, blow flies (e.g., Chrysomya spp.,Phormia spp.), and other muscoid fly pests, horse flies (e.g., Tabanusspp.), bot flies (e.g., Gastrophilus spp., Oestrus spp.), cattle grubs(e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g.,Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g.,Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimuliumspp., Simulium spp.), biting midges, sand flies, sciarids, and otherNematocera; eggs, adults and immatures of the order Thysanopteraincluding onion thrips (Thrips tabaci Lindeman), flower thrips(Frankliniella spp.), and other foliar feeding thrips; insect pests ofthe order Hymenoptera including ants of the Family Formicidae includingthe Florida carpenter ant (Camponotus floridanus Buckley), red carpenterant (Camponotus ferrugineus Fabricius), black carpenter ant (Camponotuspennsylvanicus De Geer), white-footed ant (Technomyrmex albipes fr.Smith), big headed ants (Pheidole sp.), ghost ant (Tapinomamelanocephalum Fabricius); Pharaoh ant (Monomorium pharaonic Linnaeus),little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsisgeminata Fabricius), red imported fire ant (Solenopsis invicta Buren),Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechinalongicornis Latreille), pavement ant (Tetramorium caespitum Linnaeus),cornfield ant (Lasius alienus Forster) and odorous house ant (Tapinomasessile Say). Other Hymenoptera including bees (including carpenterbees), hornets, yellow jackets, wasps, and sawflies (Neodiprion spp.;Cephus spp.); insect pests of the order Isoptera including termites inthe Termitidae (e.g., Macrotermes sp., Odontotermes obesus Rambur),Kalotermitidae (e.g., Cryptotermes sp.), and Rhinotermitidae (e.g.,Reticulitermes sp., Coptotermes sp., Heterotermes tenuis Hagen)families, the eastern subterranean termite (Reticulitermes flavipesKollar), western subterranean termite (Reticulitermes hesperus Banks),Formosan subterranean termite (Coptotermes formosanus Shiraki), WestIndian drywood termite (Incisitermes immigrans Snyder), powder posttermite (Cryptotermes brevis Walker), drywood termite (Incisitermessnyderi Light), southeastern subterranean termite (Reticulitermesvirginicus Banks), western drywood termite (Incisitermes minor Hagen),arboreal termites such as Nasutitermes sp. and other termites ofeconomic importance; insect pests of the order Thysanura such assilverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobiadomestica Packard). Additional arthropod pests covered include: spidersin the order Araneae such as the brown recluse spider (Loxoscelesreclusa Gertsch & Mulaik) and the black widow spider (Latrodectusmactans Fabricius), and centipedes in the order Scutigeromorpha such asthe house centipede (Scutigera coleoptrata Linnaeus).

Examples of invertebrate pests of stored grain include larger grainborer (Prostephanus truncatus), lesser grain borer (Rhyzoperthadominica), rice weevil (Stiophilus oryzae), maize weevil (Stiophiluszeamais), cowpea weevil (Callosobruchus maculatus), red flour beetle(Tribolium castaneum), granary weevil (Stiophilus granarius), Indianmeal moth (Plodia interpunctella), Mediterranean flour beetle (Ephestiakuhniella) and flat or rusty grain beetle (Cryptolestis ferrugineus).

Compounds of this invention have activity against pests in the orderLepidoptera (e.g., Alabama argillacea Hübner (cotton leaf worm), Archipsargyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus(European leaf roller) and other Archips species, Chilo suppressalisWalker (rice stem borer), Cnaphalocrosis medinalis Guenée (rice leafroller), Crambus caliginosellus Clemens (corn root webworm), Crambusteterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus(codling moth), Earias insulana Boisduval (spiny bollworm), Eariasvittella Fabricius (spotted bollworm), Helicoverpa armigera Hübner(American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothisvirescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker(sod webworm), Lobesia botrana Denis & Schiffermüller (grape berrymoth), Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistiscitrella Stainton (citrus leafminer), Pieris brassicae Linnaeus (largewhite butterfly), Pieris rapae Linnaeus (small white butterfly),Plutella xylostella Linnaeus (diamondback moth), Spodoptera exiguaHübner (beet armyworm), Spodoptera litura Fabricius (tobacco cutworm,cluster caterpillar), Spodoptera frugiperda J. E. Smith (fall armyworm),Trichoplusia ni Hübner (cabbage looper) and Tuta absoluta Meyrick(tomato leafminer)).

Compounds of this invention have activity against pests in the orderHomoptera including: Acyrthosiphon pisum Harris (pea aphid), Aphiscraccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid),Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer(apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solaniKaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell(strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheataphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosomalanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy(mealy plum aphid), Lipaphis erysimi Kaltenbach (turnip aphid),Metopolophium dirrhodum Walker (cereal aphid), Macrosiphum euphorbiaeThomas (potato aphid), Myzus persicae Sulzer (peach-potato aphid, greenpeach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigusspp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (cornleaf aphid), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid),Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius(English grain aphid), Therioaphis maculata Buckton (spotted alfalfaaphid), Toxoptera aurantii Boyer de Fonscolombe (black citrus aphid),and Toxoptera citricida Kirkaldy (brown citrus aphid); Adelges spp.(adelgids); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisiatabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisiaargentifolii Bellows & Perring (silverleaf whitefly), Dialeurodes citriAshmead (citrus whitefly) and Trialeurodes vaporariorum Westwood(greenhouse whitefly); Empoasca fabae Harris (potato leafhopper),Laodelphax striatellus Fallen (smaller brown planthopper), Macrolestesquadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler(green leafhopper), Nephotettix nigropictus Stâl (rice leafhopper),Nilaparvata lugens Stâl (brown planthopper), Peregrinus maidis Ashmead(corn planthopper), Sogatella furcifera Horvath (white-backedplanthopper), Sogatodes orizicola Muir (rice delphacid), Typhlocybapomaria McAtee white apple leafhopper, Erythroneoura spp. (grapeleafhoppers); Magicidada septendecim Linnaeus (periodical cicada);Icerya purchasi Maskell (cottony cushion scale), Quadraspidiotusperniciosus Comstock (San Jose scale); Planococcus citri Risso (citrusmealybug); Pseudococcus spp. (other mealybug complex); Cacopsyllapyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmonpsylla). Compounds of this invention have activity against pests in theorder Hemiptera including: Acrosternum hilare Say (green stink bug),Anasa tristis De Geer (squash bug), Blissus leucopterus leucopterus Say(chinch bug), Cimex lectularius Linnaeus (bed bug) Corythuca gossypiiFabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug),Dysdercus suturellus Herrich-Schaffer (cotton stainer), Euchistus servusSay (brown stink bug), Euchistus variolarius Palisot de Beauvois(one-spotted stink bug), Graptosthetus spp. (complex of seed bugs),Halymorpha halys Stâl (brown marmorated stink bug), Leptoglossuscorculus Say (leaf-footed pine seed bug), Lygus lineolaris Palisot deBeauvois (tarnished plant bug), Nezara viridula Linnaeus (southern greenstink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltusfasciatus Dallas (large milkweed bug), Pseudatomoscelis seriatus Reuter(cotton fleahopper). Other insect orders controlled by compounds of theinvention include Thysanoptera (e.g., Frankliniella occidentalisPergande (western flower thrips), Scirthothrips citri Moulton (citrusthrips), Sericothrips variabilis Beach (soybean thrips), and Thripstabaci Lindeman (onion thrips); and the order Coleoptera (e.g.,Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachnavarivestis Mulsant (Mexican bean beetle) and wireworms of the generaAgriotes, Athous or Limonius).

Of note is use of compounds of this invention for controllingdiamondback moth (Plutella xylostella). Of note is use of compounds ofthis invention for controlling fall armyworm (Spodoptera frugiperda). Ofnote is use of compounds of this invention for controlling westernflower thrips (Frankliniella occidentalis). Of note is use of compoundsof this invention for controlling potato leafhopper (Empoasca fabae). Ofnote is use of compounds of this invention for controlling cornplanthopper (Peregrinus maidis). Of note is use of compounds of thisinvention for controlling cotton melon aphid (Aphis gossypii). Of noteis use of compounds of this invention for controlling green peach aphid(Myzus persicae). Of note is use of compounds of this invention forcontrolling sweetpotato whitefly (Bemisia tabaci).

Compounds of the present invention may also be useful for increasingvigor of a crop plant. This method comprises contacting the crop plant(e.g., foliage, flowers, fruit or roots) or the seed from which the cropplant is grown with a compound of Formula 1 in amount sufficient toachieve the desired plant vigor effect (i.e. biologically effectiveamount). Typically the compound of Formula 1 is applied in a formulatedcomposition. Although the compound of Formula 1 is often applieddirectly to the crop plant or its seed, it can also be applied to thelocus of the crop plant, i.e. the environment of the crop plant,particularly the portion of the environment in close enough proximity toallow the compound of Formula 1 to migrate to the crop plant. The locusrelevant to this method most commonly comprises the growth medium (i.e.medium providing nutrients to the plant), typically soil in which theplant is grown. Treatment of a crop plant to increase vigor of the cropplant thus comprises contacting the crop plant, the seed from which thecrop plant is grown or the locus of the crop plant with a biologicallyeffective amount of a compound of Formula 1.

Increased crop vigor can result in one or more of the following observedeffects: (a) optimal crop establishment as demonstrated by excellentseed germination, crop emergence and crop stand; (b) enhanced cropgrowth as demonstrated by rapid and robust leaf growth (e.g., measuredby leaf area index), plant height, number of tillers (e.g., for rice),root mass and overall dry weight of vegetative mass of the crop; (c)improved crop yields, as demonstrated by time to flowering, duration offlowering, number of flowers, total biomass accumulation (i.e. yieldquantity) and/or fruit or grain grade marketability of produce (i.e.yield quality); (d) enhanced ability of the crop to withstand or preventplant disease infections and arthropod, nematode or mollusk pestinfestations; and (e) increased ability of the crop to withstandenvironmental stresses such as exposure to thermal extremes, suboptimalmoisture or phytotoxic chemicals.

The compounds of the present invention may increase the vigor of treatedplants compared to untreated plants by killing or otherwise preventingfeeding of phytophagous invertebrate pests in the environment of theplants. In the absence of such control of phytophagous invertebratepests, the pests reduce plant vigor by consuming plant tissues or sap,or transmitting plant pathogens such as viruses. Even in the absence ofphytophagous invertebrate pests, the compounds of the invention mayincrease plant vigor by modifying metabolism of plants. Generally, thevigor of a crop plant will be most significantly increased by treatingthe plant with a compound of the invention if the plant is grown in anonideal environment, i.e. an environment comprising one or more aspectsadverse to the plant achieving the full genetic potential it wouldexhibit in an ideal environment.

Of note is a method for increasing vigor of a crop plant wherein thecrop plant is grown in an environment comprising phytophagousinvertebrate pests. Also of note is a method for increasing vigor of acrop plant wherein the crop plant is grown in an environment notcomprising phytophagous invertebrate pests. Also of note is a method forincreasing vigor of a crop plant wherein the crop plant is grown in anenvironment comprising an amount of moisture less than ideal forsupporting growth of the crop plant. Of note is a method for increasingvigor of a crop plant wherein the crop is rice. Also of note is a methodfor increasing vigor of a crop plant wherein the crop is maize (corn).Also of note is a method for increasing vigor of a crop plant whereinthe crop is soybean.

Compounds of this invention can also be mixed with one or more otherbiologically active compounds or agents including insecticides,fungicides, nematocides, bactericides, acaricides, herbicides, herbicidesafeners, growth regulators such as insect molting inhibitors androoting stimulants, chemosterilants, semiochemicals, repellents,attractants, pheromones, feeding stimulants, other biologically activecompounds or entomopathogenic bacteria, virus or fungi to form amulti-component pesticide giving an even broader spectrum of agronomicand nonagronomic utility. Thus the present invention also pertains to acomposition comprising a biologically effective amount of a compound ofFormula 1, at least one additional component selected from the groupconsisting of surfactants, solid diluents and liquid diluents, and atleast one additional biologically active compound or agent. For mixturesof the present invention, the other biologically active compounds oragents can be formulated together with the present compounds, includingthe compounds of Formula 1, to form a premix, or the other biologicallyactive compounds or agents can be formulated separately from the presentcompounds, including the compounds of Formula 1, and the twoformulations combined together before application (e.g., in a spraytank) or, alternatively, applied in succession.

Examples of such biologically active compounds or agents with whichcompounds of this invention can be formulated are insecticides such asabamectin, acephate, acequinocyl, acetamiprid, acrinathrin, afidopyropen([(3S,4R,4aR,6S,6a,S,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methylcyclopropanecarboxylate), amidoflumet, amitraz, avermectin,azadirachtin, azinphos-methyl, benfuracarb, bensultap, bifenthrin,bifenazate, bistrifluron, borate, buprofezin, cadusafos, carbaryl,carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr,chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide,clofentezin, clothianidin, cyantraniliprole(3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide),cyclaniliprole (3-bromo-N-[2-bromo-4-chloro-6-[[(1cyclopropylethyl)amino]carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide),cycloprothrin, cycloxaprid((5S,8R)-1-[(6-chloro-3-pyridinyl)methyl]2,3,5,6,7,8-hexahydro-9-nitro-5,8-Epoxy-1H-imidazo[1,2-a]azepine)cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon,dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate,dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenitrothion,fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil,flometoquin(2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolinylmethyl carbonate), flonicamid, flubendiamide, flucythrinate, flufenerim,flufenoxuron, flufenoxystrobin (methyl(αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)benzeneacetate),flufensulfone(5-chloro-2-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]thiazole),fluhexafon, fluopyram, flupiprole(1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-1-yl)amino]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile),flupyradifurone(4-[[(6-chloro-3-pyridinyl)methyl](2,2-difluoroethyl)amino]-2(5H)-furanone),fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate,halofenozide, heptafluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclopropanecarboxylate),hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb,insecticidal soaps, isofenphos, lufenuron, malathion, meperfluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl(1R,3S)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate),metaflumizone, metaldehyde, methamidophos, methidathion, methiodicarb,methomyl, methoprene, methoxychlor, metofluthrin, methoxyfenozide,metofluthrin, monocrotophos, monofluorothrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl3-(2-cyano-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate),nicotine, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl,parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet,phosphamidon, pirimicarb, profenofos, profluthrin, propargite,protrifenbute, pyflubumide(1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide),pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl,pyrifluquinazon, pyriminostrobin (methyl(αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)benzeneacetate),pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram,spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos,sulfoxaflor(N-[methyloxido[1-[6-(trifluoromethyl)-3-pyridinyl]ethyl]-λ⁴-sulfanylidene]cyanamide),tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos,tetrachlorvinphos, tetramethrin, tetramethylfluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl2,2,3,3-tetramethylcyclopropanecarboxylate), tetraniliprole,thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tioxazafen(3-phenyl-5-(2-thienyl)-1,2,4-oxadiazole), tolfenpyrad, tralomethrin,triazamate, trichlorfon, triflumezopyrim(2,4-dioxo-1-(5-pyrimidinylmethyl)-3-[3-(trifluoromethyl)phenyl]-2H-pyrido[1,2-a]pyrimidiniuminner salt), triflumuron, Bacillus thuringiensis delta-endotoxins,entomopathogenic bacteria, entomopathogenic viruses and entomopathogenicfungi.

Of note are insecticides such as abamectin, acetamiprid, acrinathrin,afidopyropen, amitraz, avermectin, azadirachtin, benfuracarb, bensultap,bifenthrin, buprofezin, cadusafos, carbaryl, cartap,chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin,cyantraniliprole, cyclaniliprole, cycloprothrin, cyfluthrin,beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin,cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine,deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan,esfenvalerate, ethiprole, etofenprox, etoxazole, fenitrothion,fenothiocarb, fenoxycarb, fenvalerate, fipronil, flometoquin,flonicamid, flubendiamide, flufenoxuron, flufenoxystrobin,flufensulfone, flupiprole, flupyradifurone, fluvalinate, formetanate,fosthiazate, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid,indoxacarb, lufenuron, meperfluthrin, metaflumizone, methiodicarb,methomyl, methoprene, methoxyfenozide, metofluthrin, monofluorothrin,nitenpyram, nithiazine, novaluron, oxamyl, pyflubumide, pymetrozine,pyrethrin, pyridaben, pyridalyl, pyriminostrobin, pyriproxyfen,ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen,spirotetramat, sulfoxaflor, tebufenozide, tetramethrin,tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb,thiosultap-sodium, tralomethrin, triazamate, triflumezopyrim,triflumuron, Bacillus thuringiensis delta-endotoxins, all strains ofBacillus thuringiensis and all strains of nucleo polyhedrosis viruses.

One embodiment of biological agents for mixing with compounds of thisinvention include entomopathogenic bacteria such as Bacillusthuringiensis, and the encapsulated delta-endotoxins of Bacillusthuringiensis such as MVP® and MVPII® bioinsecticides prepared by theCellCap® process (CellCap®, MVP® and MVPII® are trademarks of MycogenCorporation, Indianapolis, Ind., USA); entomopathogenic fungi such asgreen muscardine fungus; and entomopathogenic (both naturally occurringand genetically modified) viruses including baculovirus, nucleopolyhedrovirus (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV),Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis virus(GV) such as Cydia pomonella granulosis virus (CpGV).

Of particular note is such a combination where the other invertebratepest control active ingredient belongs to a different chemical class orhas a different site of action than the compound of Formula 1. Incertain instances, a combination with at least one other invertebratepest control active ingredient having a similar spectrum of control buta different site of action will be particularly advantageous forresistance management. Thus, a composition of the present invention canfurther comprise a biologically effective amount of at least oneadditional invertebrate pest control active ingredient having a similarspectrum of control but belonging to a different chemical class orhaving a different site of action. These additional biologically activecompounds or agents include, but are not limited to,acetylcholinesterase (AChE) inhibitors such as the carbamates methomyl,oxamyl, thiodicarb, triazamate, and the organophosphates chlorpyrifos;GABA-gated chloride channel antagonists such as the cyclodienes dieldrinand endosulfan, and the phenylpyrazoles ethiprole and fipronil; sodiumchannel modulators such as the pyrethroids bifenthrin, cyfluthrin,beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin,deltamethrin, dimefluthrin, esfenvalerate, metofluthrin and profluthrin;nicotinic acetylcholinereceptor (nAChR) agonists such as theneonicotinoids acetamiprid, clothianidin, dinotefuran, imidacloprid,nitenpyram, nithiazine, thiacloprid, and thiamethoxam, and sulfoxaflor;nicotinic acetylcholine receptor (nAChR) allosteric activators such asthe spinosyns spinetoram and spinosad; chloride channel activators suchas the avermectins abamectin and emamectin; juvenile hormone mimics suchas diofenolan, methoprene, fenoxycarb and pyriproxyfen; selectivehomopteran feeding blockers such as pymetrozine and flonicamid; mitegrowth inhibitors such as etoxazole; inhibitors of mitochondrial ATPsynthase such as propargite; ucouplers of oxidative phosphorylation viadisruption of the proton gradient such as chlorfenapyr; nicotinicacetylcholine receptor (nAChR) channel blockers such as the nereistoxinanalogs cartap; inhibitors of chitin biosynthesis such as thebenzoylureas flufenoxuron, hexaflumuron, lufenuron, novaluron,noviflumuron and triflumuron, and buprofezin; dipteran moultingdisrupters such as cyromazine; ecdysone receptor agonists such as thediacylhydrazines methoxyfenozide and tebufenozide; octopamine receptoragonists such as amitraz; mitochondrial complex III electron transportinhibitors such as hydramethylnon; mitochondrial complex I electrontransport inhibitors such as pyridaben; voltage-dependent sodium channelblockers such as indoxacarb; inhibitors of acetyl CoA carboxylase suchas the tetronic and tetramic acids spirodiclofen, spiromesifen andspirotetramat; mitochondrial complex II electron transport inhibitorssuch as the β-ketonitriles cyenopyrafen and cyflumetofen; ryanidinereceptor modulators such as the anthranilic diamideschlorantraniliprole, cyantraniliprole and cyantraniliprole, diamidessuch as flubendiamide, and ryanodine receptor ligands such as ryanodine;compounds wherein the target site responsible for biological activity isunknown or uncharacterized such as azadirachtin, bifenazate, pyridalyl,pyrifluquinazon and triflumezopyrim; microbial disrupters of insectmidgut membranes such as Bacillus thuringensis and the delta-endotoxinsthey produce and Bacillus sphaericus; and biological agents includingnucleo polyhedro viruses (NPV) and other naturally occurring orgenetically modified insecticidal viruses.

Further examples of biologically active compounds or agents with whichcompounds of this invention can be formulated are: fungicides such asacibenzolar-S-methyl, aldimorph, ametoctradin, amisulbrom, anilazine,azaconazole, azoxystrobin, benalaxyl (including benalaxyl-M), benodanil,benomyl, benthiavalicarb (including benthiavalicarb-isopropyl),benzovindiflupyr, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen,blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate,carboxin, carpropamid, captafol, captan, carbendazim, chloroneb,chlorothalonil, chlozolinate, copper hydroxide, copper oxychloride,copper sulfate, coumoxystrobin, cyazofamid, cyflufenamid, cymoxanil,cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine,dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol,dimethomorph, dimoxystrobin, diniconazole (including diniconazole-M),dinocap, dithianon, dithiolanes, dodemorph, dodine, econazole,etaconazole, edifenphos, enoxastrobin (also known as enestroburin),epoxiconazole, ethaboxam, ethirimol, etridiazole, famoxadone,fenamidone, fenaminstrobin, fenarimol, fenbuconazole, fenfuram,fenhexamide, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph,fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone,flometoquin, fluazinam, fludioxonil, flufenoxystrobin, flumorph,fluopicolide, fluopyram, fluoxastrobin, fluquinconazole, flusilazole,flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet,fthalide (also known as phthalide), fuberidazole, furalaxyl, furametpyr,hexaconazole, hymexazole, guazatine, imazalil, imibenconazole,iminoctadine albesilate, iminoctadine triacetate, iodicarb, ipconazole,isofetamid, iprobenfos, iprodione, iprovalicarb, isoprothiolane,isopyrazam, isotianil, kasugamycin, kresoxim-methyl, mancozeb,mandipropamid, mandestrobin, maneb, mapanipyrin, mepronil,meptyldinocap, metalaxyl (including metalaxyl-M/mefenoxam), metconazole,methasulfocarb, metiram, metominostrobin, metrafenone, myclobutanil,naftitine, neo-asozin (ferric methanearsonate), nuarimol, octhilinone,ofurace, orysastrobin, oxadixyl, oxathiapiprolin, oxolinic acid,oxpoconazole, oxycarboxin, oxytetracycline, penconazole, pencycuron,penflufen, penthiopyrad, perfurazoate, phosphorous acid (including saltsthereof, e.g., fosetyl-aluminm), picoxystrobin, piperalin, polyoxin,probenazole, prochloraz, procymidone, propamocarb, propiconazole,propineb, proquinazid, prothiocarb, prothioconazole, pyraclostrobin,pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributacarb,pyrifenox, pyriofenone, perisoxazole, pyrimethanil, pyrifenox,pyrrolnitrin, pyroquilon, quinconazole, quinmethionate, quinoxyfen,quintozene, silthiofam, sedaxane, simeconazole, spiroxamine,streptomycin, sulfur, tebuconazole, tebufloquin, teclofthalam,tecloftalam, tecnazene, terbinafine, tetraconazole, thiabendazole,thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil,tolclofos-methyl, tolprocarb, tolyfluanid, triadimefon, triadimenol,triarimol, triazoxide, tribasic copper sulfate, triclopyricarb,tridemorph, trifloxystrobin, triflumizole, trimoprhamide tricyclazole,trifloxystrobin, triforine, triticonazole, uniconazole, validamycin,valifenalate (also known as valifenal), vinclozolin, zineb, ziram,zoxamide and1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone;nematocides such as fluopyram, spirotetramat, thiodicarb, fosthiazate,abamectin, iprodione, fluensulfone, dimethyl disulfide, tioxazafen,1,3-dichloropropene (1,3-D), metam (sodium and potassium), dazomet,chloropicrin, fenamiphos, ethoprophos, cadusaphos, terbufos, imicyafos,oxamyl, carbofuran, tioxazafen, Bacillus firmus and Pasteurianishizawae; bactericides such as streptomycin; acaricides such asamitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol,dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin,fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad.

In certain instances, combinations of a compound of this invention withother biologically active (particularly invertebrate pest control)compounds or agents (i.e. active ingredients) can result in an enhancedeffect. Reducing the quantity of active ingredients released in theenvironment while ensuring effective pest control is always desirable.When enhanced invertebrate pest control occurs at application ratesgiving agronomically satisfactory levels of invertebrate pest control,such combinations can be advantageous for reducing crop production costand decreasing environmental load.

Compounds of this invention and compositions thereof can be applied toplants genetically transformed to express proteins toxic to invertebratepests (such as Bacillus thuringiensis delta-endotoxins). Such anapplication may provide a broader spectrum of plant protection and beadvantageous for resistance management. The exogenously appliedinvertebrate pest control compounds of this invention in combinationwith the expressed toxin proteins may provide an enhanced effect.

General references for these agricultural protectants (i.e.insecticides, fungicides, nematocides, acaricides, herbicides andbiological agents) include The Pesticide Manual, 13th Edition, C. D. S.Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U. K.,2003 and The BioPesticide Manual, 2^(nd) Edition, L. G. Copping, Ed.,British Crop Protection Council, Farnham, Surrey, U. K., 2001.

Invertebrate pests are controlled in agronomic and nonagronomicapplications by applying one or more compounds of this invention,typically in the form of a composition, in a biologically effectiveamount, to the environment of the pests, including the agronomic and/ornonagronomic locus of infestation, to the area to be protected, ordirectly on the pests to be controlled.

Thus the present invention comprises a method for controlling aninvertebrate pest in agronomic and/or nonagronomic applications,comprising contacting the invertebrate pest or its environment with abiologically effective amount of one or more of the compounds of theinvention, or with a composition comprising at least one such compoundor a composition comprising at least one such compound and abiologically effective amount of at least one additional biologicallyactive compound or agent. Examples of suitable compositions comprising acompound of the invention and a biologically effective amount of atleast one additional biologically active compound or agent includegranular compositions wherein the additional active compound is presenton the same granule as the compound of the invention or on granulesseparate from those of the compound of the invention.

To achieve contact with a compound or composition of the invention toprotect a field crop from invertebrate pests, the compound orcomposition is typically applied to the seed of the crop beforeplanting, to the foliage (e.g., leaves, stems, flowers, fruits) of cropplants, or to the soil or other growth medium before or after the cropis planted.

One embodiment of a method of contact is by spraying. Alternatively, agranular composition comprising a compound of the invention can beapplied to the plant foliage or the soil. Compounds of this inventioncan also be effectively delivered through plant uptake by contacting theplant with a composition comprising a compound of this invention appliedas a soil drench of a liquid formulation, a granular formulation to thesoil, a nursery box treatment or a dip of transplants. Of note is acomposition of the present invention in the form of a soil drench liquidformulation. Also of note is a method for controlling an invertebratepest comprising contacting the invertebrate pest or its environment witha biologically effective amount of a compound of the present inventionor with a composition comprising a biologically effective amount of acompound of the present invention. Of further note is this methodwherein the environment is soil and the composition is applied to thesoil as a soil drench formulation. Of further note is that compounds ofthis invention are also effective by localized application to the locusof infestation. Other methods of contact include application of acompound or a composition of the invention by direct and residualsprays, aerial sprays, gels, seed coatings, microencapsulations,systemic uptake, baits, ear tags, boluses, foggers, fumigants, aerosols,dusts and many others. One embodiment of a method of contact is adimensionally stable fertilizer granule, stick or tablet comprising acompound or composition of the invention. The compounds of thisinvention can also be impregnated into materials for fabricatinginvertebrate control devices (e.g., insect netting).

Compounds of the invention are useful in treating all plants, plantparts and seeds. Plant and seed varieties and cultivars can be obtainedby conventional propagation and breeding methods or by geneticengineering methods. Genetically modified plants or seeds (transgenicplants or seeds) are those in which a heterologous gene (transgene) hasbeen stably integrated into the plant's or seed's genome. A transgenethat is defined by its particular location in the plant genome is calleda transformation or transgenic event.

Genetically modified plant and seed cultivars which can be treatedaccording to the invention include those that are resistant against oneor more biotic stresses (pests such as nematodes, insects, mites, fungi,etc.) or abiotic stresses (drought, cold temperature, soil salinity,etc.), or that contain other desirable characteristics. Plants and seedscan be genetically modified to exhibit traits of, for example, herbicidetolerance, insect-resistance, modified oil profiles or droughttolerance.

Treatment of genetically modified plants and seeds with compounds of theinvention may result in super-additive or enhanced effects. For example,reduction in application rates, broadening of the activity spectrum,increased tolerance to biotic/abiotic stresses or enhanced storagestability may be greater than expected from just simple additive effectsof the application of compounds of the invention on genetically modifiedplants and seeds.

Compounds of this invention are also useful in seed treatments forprotecting seeds from invertebrate pests. In the context of the presentdisclosure and claims, treating a seed means contacting the seed with abiologically effective amount of a compound of this invention, which istypically formulated as a composition of the invention. This seedtreatment protects the seed from invertebrate soil pests and generallycan also protect roots and other plant parts in contact with the soil ofthe seedling developing from the germinating seed. The seed treatmentmay also provide protection of foliage by translocation of the compoundof this invention or a second active ingredient within the developingplant. Seed treatments can be applied to all types of seeds, includingthose from which plants genetically transformed to express specializedtraits will germinate. Representative examples include those expressingproteins toxic to invertebrate pests, such as Bacillus thuringiensistoxin or those expressing herbicide resistance such as glyphosateacetyltransferase, which provides resistance to glyphosate. Seedtreatments with compounds of this invention can also increase vigor ofplants growing from the seed.

One method of seed treatment is by spraying or dusting the seed with acompound of the invention (i.e. as a formulated composition) beforesowing the seeds. Compositions formulated for seed treatment generallycomprise a film former or adhesive agent. Therefore typically a seedcoating composition of the present invention comprises a biologicallyeffective amount of a compound of Formula 1, and a film former oradhesive agent. Seed can be coated by spraying a flowable suspensionconcentrate directly into a tumbling bed of seeds and then drying theseeds. Alternatively, other formulation types such as wetted powders,solutions, suspoemulsions, emulsifiable concentrates and emulsions inwater can be sprayed on the seed. This process is particularly usefulfor applying film coatings on seeds. Various coating machines andprocesses are available to one skilled in the art. Suitable processesinclude those listed in P. Kosters et al., Seed Treatment: Progress andProspects, 1994 BCPC Mongraph No. 57, and references listed therein.

Compounds of Formula 1 and their compositions, both alone and incombination with other insecticides, nematicides, and fungicides, areparticularly useful in seed treatment for crops including, but notlimited to, maize or corn, soybeans, cotton, cereal (e.g., wheat, oats,barley, rye and rice), potatoes, vegetables and oilseed rape.

Other insecticides with which compounds of Formula 1 can be formulatedto provide mixtures useful in seed treatment include abamectin,acetamiprid, acrinathrin, amitraz, avermectin, azadirachtin, bensultap,bifenthrin, buprofezin, cadusafos, carbaryl, carbofuran, cartap,chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin,cyantraniliprole, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran,diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox,etoxazole, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flonicamid,flubendiamide, flufenoxuron, fluvalinate, formetanate, fosthiazate,hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron,metaflumizone, methiocarb, methomyl, methoprene, methoxyfenozide,nitenpyram, nithiazine, novaluron, oxamyl, pymetrozine, pyrethrin,pyridaben, pyridalyl, pyriproxyfen, ryanodine, spinetoram, spinosad,spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide,tetramethrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium,tralomethrin, triazamate, triflumuron, Bacillus thuringiensisdelta-endotoxins, all strains of Bacillus thuringiensis and all strainsof nucleo polyhedrosis viruses.

Fungicides with which compounds of Formula 1 can be formulated toprovide mixtures useful in seed treatment include amisulbrom,azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil, cyproconazole,difenoconazole, dimethomorph, fluazinam, fludioxonil, fluquinconazole,fluopicolide, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole,iprodione, metalaxyl, mefenoxam, metconazole, myclobutanil,paclobutrazole, penflufen, picoxystrobin, prothioconazole,pyraclostrobin, sedaxane, silthiofam, tebuconazole, thiabendazole,thiophanate-methyl, thiram, trifloxystrobin and triticonazole.

Compositions comprising compounds of Formula 1 useful for seed treatmentcan further comprise bacteria and fungi that have the ability to provideprotection from the harmful effects of plant pathogenic fungi orbacteria and/or soil born animals such as nematodes. Bacteria exhibitingnematicidal properties may include but are not limited to Bacillusfirmus, Bacillus cereus, Bacillius subtiliis and Pasteuria penetrans. Asuitable Bacillus firmus strain is strain CNCM 1-1582 (GB-126) which iscommercially available as BioNem™. A suitable Bacillus cereus strain isstrain NCMM 1-1592. Both Bacillus strains are disclosed in U.S. Pat. No.6,406,690.

Other suitable bacteria exhibiting nematicidal activity are B.amyloliquefaciens IN937a and B. subtilis strain GB03. Bacteriaexhibiting fungicidal properties may include but are not limited to B.pumilus strain GB34. Fungal species exhibiting nematicidal propertiesmay include but are not limited to Myrothecium verrucaria, Paecilomyceslilacinus and Purpureocillium lilacinum.

Seed treatments can also include one or more nematicidal agents ofnatural origin such as the elicitor protein called harpin which isisolated from certain bacterial plant pathogens such as Erwiniaamylovora. An example is the Harpin-N-Tek seed treatment technologyavailable as N-Hibit™ Gold CST.

Seed treatments can also include one or more species of legume-rootnodulating bacteria such as the microsymbiotic nitrogen-fixing bacteriaBradyrhizobium japonicum. These inocculants can optionally include oneor more lipo-chitooligosaccharides (LCOs), which are nodulation (Nod)factors produced by rhizobia bacteria during the initiation of noduleformation on the roots of legumes. For example, the Optimize® brand seedtreatment technology incorporates LCO Promoter Technology™ incombination with an inocculant.

Seed treatments can also include one or more isoflavones which canincrease the level of root colonization by mycorrhizal fungi.Mycorrhizal fungi improve plant growth by enhancing the root uptake ofnutrients such as water, sulfates, nitrates, phosphates and metals.Examples of isoflavones include, but are not limited to, genistein,biochanin A, formononetin, daidzein, glycitein, hesperetin, naringeninand pratensein. Formononetin is available as an active ingredient inmycorrhizal inocculant products such as PHC Colonize® AG.

Seed treatments can also include one or more plant activators thatinduce systemic acquired resistance in plants following contact by apathogen. An example of a plant activator which induces such protectivemechanisms is acibenzolar-S-methyl.

The treated seed typically comprises a compound of the present inventionin an amount from about 0.1 g to 1 kg per 100 kg of seed (i.e. fromabout 0.0001 to 1% by weight of the seed before treatment). A flowablesuspension formulated for seed treatment typically comprises from about0.5 to about 70% of the active ingredient, from about 0.5 to about 30%of a film-forming adhesive, from about 0.5 to about 20% of a dispersingagent, from 0 to about 5% of a thickener, from 0 to about 5% of apigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0to about 1% of a preservative, and from 0 to about 75% of a volatileliquid diluent.

The compounds of this invention can be incorporated into a baitcomposition that is consumed by an invertebrate pest or used within adevice such as a trap, bait station, and the like. Such a baitcomposition can be in the form of granules which comprise (a) activeingredients, namely a biologically effective amount of a compound ofFormula 1; (b) one or more food materials; optionally (c) an attractant,and optionally (d) one or more humectants. Of note are granules or baitcompositions which comprise between about 0.001-5% active ingredients,about 40-99% food material and/or attractant; and optionally about0.05-10% humectants, which are effective in controlling soilinvertebrate pests at very low application rates, particularly at dosesof active ingredient that are lethal by ingestion rather than by directcontact. Some food materials can function both as a food source and anattractant. Food materials include carbohydrates, proteins and lipids.Examples of food materials are vegetable flour, sugar, starches, animalfat, vegetable oil, yeast extracts and milk solids. Examples ofattractants are odorants and flavorants, such as fruit or plantextracts, perfume, or other animal or plant component, pheromones orother agents known to attract a target invertebrate pest. Examples ofhumectants, i.e. moisture retaining agents, are glycols and otherpolyols, glycerine and sorbitol. Of note is a bait composition (and amethod utilizing such a bait composition) used to control at least oneinvertebrate pest selected from the group consisting of ants, termitesand cockroaches. A device for controlling an invertebrate pest cancomprise the present bait composition and a housing adapted to receivethe bait composition, wherein the housing has at least one opening sizedto permit the invertebrate pest to pass through the opening so theinvertebrate pest can gain access to the bait composition from alocation outside the housing, and wherein the housing is further adaptedto be placed in or near a locus of potential or known activity for theinvertebrate pest.

One embodiment of the present invention relates to a method forcontrolling invertebrate pests, comprising diluting the pesticidalcomposition of the present invention (a compound of Formula 1 formulatedwith surfactants, solid diluents and liquid diluents or a formulatedmixture of a compound of Formula 1 and at least one other pesticide)with water, and optionally adding an adjuvant to form a dilutedcomposition, and contacting the invertebrate pest or its environmentwith an effective amount of said diluted composition.

Although a spray composition formed by diluting with water a sufficientconcentration of the present pesticidal composition can providesufficient efficacy for controlling invertebrate pests, separatelyformulated adjuvant products can also be added to spray tank mixtures.These additional adjuvants are commonly known as “spray adjuvants” or“tank-mix adjuvants”, and include any substance mixed in a spray tank toimprove the performance of a pesticide or alter the physical propertiesof the spray mixture. Adjuvants can be surfactants, emulsifying agents,petroleum-based crop oils, crop-derived seed oils, acidifiers, buffers,thickeners or defoaming agents. Adjuvants are used to enhancing efficacy(e.g., biological availability, adhesion, penetration, uniformity ofcoverage and durability of protection), or minimizing or eliminatingspray application problems associated with incompatibility, foaming,drift, evaporation, volatilization and degradation. To obtain optimalperformance, adjuvants are selected with regard to the properties of theactive ingredient, formulation and target (e.g., crops, insect pests).

Among the spray adjuvants, oils including crop oils, crop oilconcentrates, vegetable oil concentrates and methylated seed oilconcentrates are most commonly used to improve the efficacy ofpesticides, possibly by means of promoting more even and uniform spraydeposits. In situations where phytotoxicity potentially caused by oilsor other water-immiscible liquids are of concern, spray compositionsprepared from the composition of the present invention will generallynot contain oil-based spray adjuvants. However, in situations wherephytotoxicity caused by oil-based spray adjuvants is commerciallyinsignificant, spray compositions prepared from the composition of thepresent composition can also contain oil-based spray adjuvants, whichcan potentially further increase control of invertebrate pests, as wellas rainfastness.

Products identified as “crop oil” typically contain 95 to 98% paraffinor naphtha-based petroleum oil and 1 to 2% of one or more surfactantsfunctioning as emulsifiers. Products identified as “crop oilconcentrates” typically consist of 80 to 85% of emulsifiablepetroleum-based oil and 15 to 20% of nonionic surfactants. Productscorrectly identified as “vegetable oil concentrates” typically consistof 80 to 85% of vegetable oil (i.e. seed or fruit oil, most commonlyfrom cotton, linseed, soybean or sunflower) and 15 to 20% of nonionicsurfactants. Adjuvant performance can be improved by replacing thevegetable oil with methyl esters of fatty acids that are typicallyderived from vegetable oils. Examples of methylated seed oilconcentrates include MSO® Concentrate (UAP-Loveland Products, Inc.) andPremium MSO Methylated Spray Oil (Helena Chemical Company).

The amount of adjuvants added to spray mixtures generally does notexceed about 2.5% by volume, and more typically the amount is from about0.1 to about 1% by volume. The application rates of adjuvants added tospray mixtures are typically between about 1 to 5 L per hectare.Representative examples of spray adjuvants include: Adigor® (Syngenta)47% methylated rapeseed oil in liquid hydrocarbons, Silwet® (HelenaChemical Company) polyalkyleneoxide modified heptamethyltrisiloxane andAssist® (BASF) 17% surfactant blend in 83% paraffin based mineral oil.

The compounds of this invention can be applied without other adjuvants,but most often application will be of a formulation comprising one ormore active ingredients with suitable carriers, diluents, andsurfactants and possibly in combination with a food depending on thecontemplated end use. One method of application involves spraying awater dispersion or refined oil solution of a compound of the presentinvention. Combinations with spray oils, spray oil concentrations,spreader stickers, adjuvants, other solvents, and piperonyl butoxideoften enhance compound efficacy. For nonagronomic uses such sprays canbe applied from spray containers such as a can, a bottle or othercontainer, either by means of a pump or by releasing it from apressurized container, e.g., a pressurized aerosol spray can. Such spraycompositions can take various forms, for example, sprays, mists, foams,fumes or fog. Such spray compositions thus can further comprisepropellants, foaming agents, etc. as the case may be. Of note is a spraycomposition comprising a biologically effective amount of a compound ora composition of the present invention and a carrier. One embodiment ofsuch a spray composition comprises a biologically effective amount of acompound or a composition of the present invention and a propellant.Representative propellants include, but are not limited to, methane,ethane, propane, butane, isobutane, butene, pentane, isopentane,neopentane, pentene, hydrofluorocarbons, chlorofluorocarbons, dimethylether, and mixtures of the foregoing. Of note is a spray composition(and a method utilizing such a spray composition dispensed from a spraycontainer) used to control at least one invertebrate pest selected fromthe group consisting of mosquitoes, black flies, stable flies, deerflies, horse flies, wasps, yellow jackets, hornets, ticks, spiders,ants, gnats, and the like, including individually or in combinations.

The following Tests demonstrate the control efficacy of compounds ofthis invention on specific pests. “Control efficacy” representsinhibition of invertebrate pest development (including mortality) thatcauses significantly reduced feeding. The pest control protectionafforded by the compounds is not limited, however, to these species. SeeIndex Tables A-G for compound descriptions.

BIOLOGICAL EXAMPLES OF THE INVENTION

Formulation and Spray Methodology for Tests A-H

Test compounds were formulated using a solution containing 10% acetone,90% water and 300 ppm Activator 90® non-ionic surfactant (LovelandProducts, Loveland, Colo., USA). The formulated compounds were appliedin 1 mL of liquid through an atomizer nozzle positioned 1.27 cm (0.5inches) above the top of each test unit. Test compounds were sprayed atthe rates indicated, and each test was replicated three times.

Test A

For evaluating control of diamondback moth (Plutella xylostella (L.))the test unit consisted of a small open container with a 12-14-day-oldmustard plant inside. This was pre-infested with ˜50 neonate larvae thatwere dispensed into the test unit via corn cob grits using aninoculator. The larvae moved onto the test plant after being dispensedinto the test unit.

Test compounds were formulated and sprayed at 250, 50, 10 and 2 ppm.After spraying of the formulated test compound, each test unit wasallowed to dry for 1 hour and then a black, screened cap was placed ontop. The test units were held for 6 days in a growth chamber at 25° C.and 70% relative humidity. Plant feeding damage was then visuallyassessed based on foliage consumed, and larvae were assessed formortality.

Of the compounds of Formula 1 tested at 250 ppm, the following providedvery good to excellent levels of control efficacy (40% or less feedingdamage and/or 100% mortality): 1, 2, 10, 34, 35, 39 and 40.

Of the compounds of Formula 1 tested at 50 ppm, the following providedvery good to excellent levels of control efficacy (40% or less feedingdamage and/or 100% mortality): 1, 2, 10, 34, 35, 39 and 40.

Of the compounds of Formula 1 tested at 10 ppm, the following providedvery good to excellent levels of control efficacy (40% or less feedingdamage and/or 100% mortality): 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 12, 13,14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31,32, 33, 34, 35, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 52, 53,54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 65, 70, 71, 72, 73, 74, 75, 76,77, 78 and 79.

Of the compounds of Formula 1 tested at 2 ppm, the following providedvery good to excellent levels of control efficacy (40% or less feedingdamage and/or 100% mortality): 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 12, 13,14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 26, 27, 28, 29, 30, 31, 33, 34,35, 39, 40, 41, 43, 44, 45, 46, 47, 48, 49, 50, 52, 53, 55, 56, 58, 59,60, 61, 63, 65, 70, 71, 72, 73, 74, 75, 76, 77, 78 and 79.

Test B For evaluating control of fall armyworm (Spodoptera frugiperda(J. E. Smith)) the test unit consisted of a small open container with a4-5-day-old corn (maize) plant inside. This was pre-infested with 10-151-day-old larvae on a piece of insect diet.

Test compounds were formulated and sprayed at 250, 50, 10 and 2 ppm.After spraying of the formulated test compound, the test units weremaintained in a growth chamber for 6 days at 25° C. and 70% relativehumidity. Plant feeding damage was then visually assessed based onfoliage consumed, and larvae were assessed for mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following providedvery good to excellent levels of control efficacy (40% or less feedingdamage and/or 100% mortality): 1, 2, 10, 34, 35, 39 and 40.

Of the compounds of Formula 1 tested at 50 ppm, the following providedvery good to excellent levels of control efficacy (40% or less feedingdamage and/or 100% mortality): 1, 2, 10, 34, 35, 39 and 40.

Of the compounds of Formula 1 tested at 10 ppm, the following providedvery good to excellent levels of control efficacy (40% or less feedingdamage and/or 100% mortality): 1, 2, 3, 4, 6, 7, 8, 10, 11, 12, 13, 14,15, 16, 17, 18, 19, 20, 22, 23, 24, 27, 28, 29, 30, 31, 33, 34, 39, 41,43, 44, 45, 46, 47, 48, 49, 50, 52, 55, 58, 59, 60, 61, 63, 65, 70, 71,72, 73, 74, 75, 76, 77, 78 or 79.

Of the compounds of Formula 1 tested at 2 ppm, the following providedvery good to excellent levels of control efficacy (40% or less feedingdamage and/or 100% mortality): 1, 2, 3, 4, 8, 10, 11, 13, 15, 16, 18,19, 20, 33, 34, 39, 43, 46, 49, 50, 59, 60, 61, 63, 65, 70, 71, 74, 76,78 or 79.

Test C

For evaluating control of corn planthopper (Peregrinus maidis (Ashmead))through contact and/or systemic means, the test unit consisted of asmall open container with a 3-4-day-old corn (maize) plant inside. Whitesand was added to the top of the soil prior to application of the testcompound.

Test compounds were formulated and sprayed at 50 ppm. After spraying ofthe formulated test compound, the test units were allowed to dry for 1 hbefore they were post-infested with ˜15-20 nymphs (18-to-21-day-old). Ablack, screened cap was placed on the top of each test unit, and thetest units were held for 6 days in a growth chamber at 22-24° C. and50-70% relative humidity. Each test unit was then visually assessed forinsect mortality.

Of the compounds of Formula 1 tested at 50 ppm, the following resultedin at least 80% mortality: 11, 44, 46, 60, 61 and 63.

Test D

For evaluating control of potato leafhopper (Empoasca fabae (Harris))through contact and/or systemic means, the test unit consisted of asmall open container with a 5-6-day-old Soleil bean plant (primaryleaves emerged) inside. White sand was added to the top of the soil, andone of the primary leaves was excised prior to application of the testcompound.

Test compounds were formulated and sprayed at 250, 50, 10 and 2 ppm.After spraying of the formulated test compound, the test units wereallowed to dry for 1 hour before they were post-infested with 5 potatoleafhoppers (18-to-21-day-old adults). A black, screened cap was placedon the top of the test unit, and the test units were held for 6 days ina growth chamber at 20° C. and 70% relative humidity. Each test unit wasthen visually assessed for insect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following resultedin at least 80% mortality: 1, 2, 10, 34, 35, 39 and 40.

Of the compounds of Formula 1 tested at 50 ppm, the following resultedin at least 80% mortality: 1, 2, 3, 4, 5, 8, 10, 11, 12, 13, 14, 15, 16,17, 18, 19, 20, 27, 31, 33, 34, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48,49, 50, 52, 53, 55, 58, 59, 60, 61, 63, 65, 70, 71, 72, 75, 76, 78 or79.

Of the compounds of Formula 1 tested at 10 ppm, the following resultedin at least 80% mortality: 3, 4, 8, 10, 11, 13, 14, 15, 16, 18, 19, 20,27, 33, 41, 43, 44, 47, 48, 49, 50, 52, 58, 59, 60, 61, 63, 65, 70, 71,72, 75, 76, 78, 79.

Of the compounds of Formula 1 tested at 2 ppm, the following resulted inat least 80% mortality: 15, 16, 18, 20, 33, 61 and 63.

Test E

For evaluating control of green peach aphid (Myzus persicae (Sulzer))through contact and/or systemic means, the test unit consisted of asmall open container with a 12-15-day-old radish plant inside. This waspre-infested by placing on a leaf of the test plant 30-40 aphids on apiece of leaf excised from a culture plant (cut-leaf method). The aphidsmoved onto the test plant as the leaf piece desiccated. Afterpre-infestation, the soil of the test unit was covered with a layer ofsand.

Test compounds were formulated and sprayed at 250, 50 and 10 ppm. Afterspraying of the formulated test compound, each test unit was allowed todry for 1 hour and then a black, screened cap was placed on top. Thetest units were held for 6 days in a growth chamber at 19-21° C. and50-70% relative humidity. Each test unit was then visually assessed forinsect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following resultedin at least 80% mortality: 2, 10, 34 and 35.

Of the compounds of Formula 1 tested at 50 ppm, the following resultedin at least 80% mortality: 3, 4, 8, 11, 18, 19, 20, 33, 34, 35, 41, 44,50, 58, 60, 61, 63 and 70.

Of the compounds of Formula 1 tested at 10 ppm, the following resultedin at least 80% mortality: 61 and 63.

Test F

For evaluating control of cotton melon aphid (Aphis gossypii (Glover))through contact and/or systemic means, the test unit consisted of asmall open container with a 5-day-old okra plant inside. This waspre-infested with 30-40 insects on a piece of leaf according to thecut-leaf method, and the soil of the test unit was covered with a layerof sand.

Test compounds were formulated and sprayed at 250, 50 and 10 ppm. Afterspraying, the test units were maintained in a growth chamber for 6 daysat 19° C. and 70% relative humidity. Each test unit was then visuallyassessed for insect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following resultedin at least 80% mortality: 1, 2, 10, 34, 35 and 39.

Of the compounds of Formula 1 tested at 50 ppm, the following resultedin at least 80% mortality: 3, 4, 8, 10, 11, 16, 18, 19, 20, 22, 33, 34,35, 41, 44, 46, 47, 49, 50, 55, 58, 59, 60, 61, 63 and 70.

Of the compounds of Formula 1 tested at 10 ppm, the following resultedin at least 80% mortality: 19, 20, 33, 41, 44, 59, 60, 61, 63 and 70.

Test G

For evaluating control of the sweetpotato whitefly (Bemisia tabaci(Gennadius)) through contact and/or systemic means, the test unitconsisted of a small open container with a 12-14-day-old cotton plantinside. Prior to the spray application, both cotyledons were removedfrom the plant, leaving one true leaf for the assay. Adult whiteflieswere allowed to lay eggs on the plant and then were removed from thetest unit. Cotton plants infested with at least 15 eggs were submittedto the test for spraying.

Test compounds were formulated and sprayed at 250, 50, and 10 ppm. Afterspraying, the test units were allowed to dry for 1 hour. The cylinderswere then removed, and the units were taken to a growth chamber and heldfor 13 days at 28° C. and 50-70% relative humidity. Each test unit wasthen visually assessed for insect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following resultedin at least 70% mortality: 2, 34 and 40.

Of the compounds of Formula 1 tested at 50 ppm, the following resultedin at least 70% mortality: 3, 8, 11, 15, 17, 18, 19, 20, 33, 34, 41, 42,44, 46, 49, 55, 58, 60, 61, 63 and 70.

Of the compounds of Formula 1 tested at 10 ppm, the following resultedin at least 70% mortality: 8, 11, 18, 19, 20, 33, 34, 42, 49, 61 and 63.

Of the compounds of Formula 1 tested at 2 ppm, the following resulted inat least 70% mortality: 18, 20, 33 and 63.

Test H

For evaluating control of the Western Flower Thrips (Franklinielllaoccidentalis (Pergande)) through contact and/or systemic means, the testunit consisted of a small open container with a 5-7-day-old Soleil beanplant inside.

Test compounds were formulated and sprayed at 250, 50, 10 and 2 ppm.After spraying, the test units were allowed to dry for 1 hour, and then˜60 thrips (adults and nymphs) were added to each unit. A black,screened cap was placed on top, and the test units were held for 6 daysat 25° C. and 45-55% relative humidity. Each test unit was then visuallyassessed for plant damage and insect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following providedvery good to excellent levels of control efficacy (30% or less plantdamage and/or 100% mortality): 1, 2, 10, 34, 35, 39 and 40.

Of the compounds of Formula 1 tested at 50 ppm, the following providedvery good to excellent levels of control efficacy (30% or less plantdamage and/or 100% mortality): 1, 10, 34, 35, 39 and 40.

Of the compounds of Formula 1 tested at 10 ppm, the following providedvery good to excellent levels of control efficacy (30% or less plantdamage and/or 100% mortality): 1, 3, 4, 5, 7, 8, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20, 21, 22, 23, 25, 26, 27, 28, 29, 31, 33, 34, 39, 41,43, 44, 45, 46, 47, 48, 49, 50, 58, 59, 60, 61, 63, 65, 70, 71, 72, 73,74, 75, 76, 78 and 79.

Of the compounds of Formula 1 tested at 2 ppm, the following providedvery good to excellent levels of control efficacy (30% or less plantdamage and/or 100% mortality): 3, 4, 8, 10, 11, 13, 14, 16, 19, 20, 22,26, 27, 33, 34, 39, 43, 44, 46, 47, 50, 59, 60, 61, 63, 70, 71, 72, 73,74, 75, 76, 78 and 79.

What is claimed is:
 1. A compound selected from Formula 1,

wherein J is

R^(1a) is Cl or CF₃; R^(1b) is H or Cl; R² is C₁-C₄ alkyl, unsubstituted or substituted with substituents independently selected from cyano, nitro, and OR⁹; R³ is H; or C₁-C₄ alkyl, unsubstituted or substituted with substituents independently selected from cyano, nitro, and OR⁹; R⁴ is H, C₁-C₄ alkyl or C₁-C₄ haloalkyl; each R⁹ is H or C₁-C₄ alkyl; each n is independently 0, 1 or
 2. 2. The compound of claim 1 wherein R² is methyl; R³ is H or methyl; and R⁴ is H or methyl.
 3. A composition comprising a compound of claim 1 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, said composition optionally further comprising at least one additional biologically active compound or agent.
 4. The composition of claim 3 wherein the at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, afidopyropen, amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, benfuracarb, bensultap, bifenthrin, bifenazate, bistrifluron, borate, buprofezin, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cycloxaprid, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flucythrinate, flufenerim, flufenoxuron, flufenoxystrobin, flufensulfone, fluorpyram, flupiprole, flupyradifurone, fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate, halofenozide, heptafluthrin, hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soaps, isofenphos, lufenuron, malathion, meperfluthrin, metaflumizone, metaldehyde, methamidophos, methidathion, methiodicarb, methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos, monofluthrin, methoxyfenozide, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite, protrifenbute, pyflubumide, pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl, pyrifluquinazon, pyriminostrobin, pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos, sulfoxaflor, tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate, trichlorfon, triflumuron, all strains of Bacillus thuringiensis, entomopathogenic bacteria, all strains of Nucleo polyhedrosis viruses, entomopathogenic viruses and entomopathogenic fungi.
 5. The composition of claim 4 wherein the at least one additional biologically active compound or agent is selected from the group consisting of abamectin, acetamiprid, acrinathrin, afidopyropen, amitraz, avermectin, azadirachtin, benfuracarb, bensultap, bifenthrin, 3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide, buprofezin, carbaryl, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole, fenitrothion, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flometoquin, flonicamid, flubendiamide, flufenoxuron, flufenoxystrobin, flufensulfone, flupiprole, flupyradifurone, fluvalinate, formetanate, fosthiazate, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron, meperfluthirn, metaflumizone, methiodicarb, methomyl, methoprene, methoxyfenozide, metofluthrin, monofluthrin, nitenpyram, nithiazine, novaluron, oxamyl, pyflubumide, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriminostrobin, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, tetramethylfluthrin, triazamate, triflumuron, all strains of Bacillus thuringiensis and all strains of Nucleo polyhedrosis viruses.
 6. A method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of claim
 1. 7. A treated seed comprising a compound of claim 1 in an amount of from about 0.0001 to 1% by weight of the seed before treatment. 